The 27-year-old will step out on Centre Court to launch his challenge for a second title against Belgium's David Goffin.
Murray will be hoping to clinch the Wimbledon two-in-a-row following his historic victory last summer against Novak Djokovic.
Having ended the wait for a British male singles champion at Wimbledon after 77 years, Murray will try to emulate Fred Perry once more by retaining the title.
One of Murray's biggest fans was at the front of the queue, having arrived at the venue at 7.30am on Saturday.
Stuart Bere, 39, a gardener from Lincolnshire, has booked the next two weeks off work.
He said of the queue: "It's buzzing. It's the best atmosphere it's been for years. The time just flew by and, to be honest, you're just chilling out."
Mr Bere drove to Wimbledon with his car packed up like he was "going on holiday".
Well prepared, he has been feasting on rice and fish cooked on a portable stove.
After spending Saturday night on the pavement, and last night in a tent, Mr Bere said he was feeling fine.
"I've been sleeping. Now that I've had a coffee, I feel awake," he said.
Mr Bere said it was all worth it.
"We're going to see a British Wimbledon champion walk out (on Centre Court), which will be amazing," he said.
One woman who has been in the queue since 10am on Saturday is hoping for a double celebration.
Linda Loader, a lab technician from Yateley in Hampshire, is 58 today, and hopes that she will be celebrating not only her birthday but a Murray win as well.
She has followed the Scot's career "right from the start", and said she gets emotional just thinking about his successes.
After spending the last two nights in Wimbledon, she joked she was coping well "for a 58-year-old".
Ms Loader watched last year's historic final on television and said she and her friends sent text messages to each other throughout.
She is joined by her sisters-in-law Sandie Bishop, 47, also from Yateley, and Chris Allen, 57, from Cornwall.
Ms Allen said: "You're just running on adrenaline."
Birthday girl Ms Loader is looking forward to her time on Centre Court, and said: "I think it's going to be exciting from the point of view that so many people are going to be there."
Asked how he felt about having the hopes of a nation on his shoulders going into the 2014 championships, Murray said: "Wow."
But the Wimbledon champion is focused only on his own game.
"I'm here to try and win the tournament. That's it. My focus is solely on the first match, preparing properly for that," he said at a press conference yesterday.
"So I believe if I play my best tennis, I'll give myself a chance of doing well here. You know, putting myself in a position to win the tournament.
"But you can't start off slowly in these tournaments. You need to try and be on it from the first match. I'll be ready."
Tickets for Centre Court and Court Number One were sold out by about 8.30am yesterday.
With the World Cup taking place in Brazil, tennis is not the only sport this summer - but England are now out of the competition and will fly home early, dashing the dreams of thousands.
Despite sporting fans having one eye on the action in Brazil, the World Cup will not be shown on screens at the All England Club.
A spokesman said the last time they showed football was in 1996 - "so very consistent since then".
Murray was asked what he thought of England's performance in Brazil.
He said: "I don't think they played too badly, to be honest. I think the first match against Italy was probably better than Uruguay.
"But, yeah, I like football. I watch a lot of football. I enjoy it when the World Cup is on. It gives me something to do in the evenings.
"I don't have to listen to people talking about me playing at Wimbledon. I can just watch the football. Don't need to worry about any of that stuff."
The Wimbledon champion said the World Cup is likely to be a big talking point among tennis players over the next fortnight.
"Pretty much when you walk into the locker room most mornings, that's what almost all of the players are talking about, really.
"A lot of the Spanish guys have been a little bit quiet the last few days. But, yeah, it's nice.
"That's one of the good things about tennis. It's such a global sport. I don't know how many countries there will be involved in the Championships this year, but so many of them.
"When you've got a competition like the World Cup on, everyone takes an interest."
Murray said he is feeling "nervous" going into Wimbledon, adding: "But I think, you know, always when you come back to a Grand Slam, there's always nerves and pressure there before you start the event. I feel fairly similar to last year."
Despite the summery weather over the last few days, forecasters say the opening day of the tournament could see interruptions in the afternoon due to rain.
Simon Partridge, a forecaster at the Met Office, said yesterday: "It's going to be OK, very similar day on Monday from today, so plenty of dry, sunny weather around throughout the morning.
"We expect temperatures throughout to be again quite similar to today, so 24C/25C."
But Mr Partridge said there is a chance of some showers developing through the afternoon, with a 30% chance of a shower from mid-afternoon onwards, and 20% chance of it being a heavy shower.
Bookmaker William Hill is offering odds of 3/1 for a Murray victory, while Novak Djokovic is favourite on 7/4.
Rafael Nadal, who goes into Wimbledon as the French Open champion, is 9/2 to win, and Roger Federer is on 5/1.
William Hill is offering odds of 5/4 on Serena Williams to win, 5/1 on a Maria Sharapova victory and 150/1 on a Watson win.
Murray, who was awarded an OBE in the new year honours list in December 2012, has an Olympic gold medal after beating Federer at London 2012 and silverware from the US Open after beating Djokovic in the same year.
The British number one parted company with his coach Ivan Lendl in March and has brought in former Wimbledon women's champion Amelie Mauresmo to replace him, initially on a short-term basis.
It has made him the highest-profile man in the sport to appoint a female coach.
Lee Dunning, a 36-year-old sales assistant from Manchester, has also booked the next fortnight off.
"I do see it as my summer break," he said.
Mr Dunning arrived with his friend John Mulroy, 51, at 8.30am yesterday and both men said their predictions that the World Cup would cut the length of the queue were proved incorrect.
Mr Mulroy said: "We couldn't have physically got here any quicker yesterday and we're still number 630 in the queue."
Mr Dunning said his friends question his love for Wimbledon and call tennis "that elitist sport".
"That's what I like about it. The tradition of it," he said.
One of the oldest people to camp out for a ticket is 70-year-old Angela Spencer, from Woodstock in Oxfordshire.
The pensioner, who has come to the event alone, hailed the "absolutely brilliant organisation" at the tournament and in the queue.
Ms Spencer arrived in Wimbledon at 7pm yesterday and has missed out on a coveted Centre Court ticket, but is looking forward to the atmosphere on Murray Mount.
Asked what her family and friends thought about her solo tennis adventure, she said: "They're used to me camping out and doing daft things. I just enjoy this sort of thing."
Ms Spencer said she has become a Murray fan in the last year or so, "when his attitude has mellowed".
Friends Dave Jackson, 33, and Jackson Todd, 31, from Belfast, arrived last night at 9pm.
Mr Jackson, who was at Wimbledon in 2010 - a year when the World Cup was also on at the same time - said he found this year's queue "so much busier".
He said of the tournament: "It's cool now. It's just very cool. It's chic. It's fashionable. Before, it would have been tennis fans."
Mr Todd said he is looking forward to people-watching.
Murray will have a fan in the grounds all the way from the Philippines.
Richie Tolenada, 46, lives in London and is "a big tennis fan".
He arrived this morning at 3am in a bid to secure a ticket and said he will be cheering for the Scot.
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