Revealed, which brings together over 160 works from the 13,000-plus UK Government Art Collection, have until now been largely hidden from public view on the walls of offices and embassies across the UK and beyond.
And, in an engaging twist, many of the taxpayer-funded works on display have been picked by the very people who have worked under their gaze, from Deputy Prime Minister Nick Clegg to one of the 10 Downing Street cleaners.
As well as opening out the collection to the public who own it, the exhibition gives a unique insight into the role played by art in cultural diplomacy. Pieces will have spent time in cities as far apart as Mexico and Rome. The works on display include paintings from the 1500s to the collection's most recent commission, Prepared Pianola for Roger Bannister, which was created to celebrate the 2012 London Olympics.
"It's incredibly exciting to see my work here," said artist Mel Brimfield.
"It's a peculiar context for an artist for a piece of work having to be diplomatic. But then you think about what a lot of these works have witnessed over the years."
Although this is the first time the works have been presented in such a large exhibition, organisers are hopeful that there may be scope for future such displays.
"We were going for 113 years before we had our first exhibition, not for the lack of wanting to have one," explains Penny Johnson (left), director of the collection.
"There has been much more of an emphasis now, not just with the art collection, on making things more accessible and transparent, so we'll hopefully do smaller exhibitions, but perhaps not one on this scale again.
"The juxtaposition of historical and modern and contemporary beside each other is something that is particular to this exhibition. It says that the art of the UK is incredibly creative, across five centuries."
Where else would you find Cromwell beside Charles I? Matthew McCreary views the exhibits
They are perhaps the ultimate ice-breakers... and who knows what earth-shattering deals have been struck by world leaders under their watchful gaze?
The breadth of pieces on display in this exhibition is truly breathtaking, so perhaps entrusting at least part of such an overwhelming task to the people who have lived and worked with them is certainly a novel way to do it.
And the real key to this exhibition's success is in way it has been curated. With less care, works as varied as these might well have been lumped in by historical period, by geographical reference or artistic genre.
But to see a 16th century portrait of Henry VI hanging a whisker away from a neon sign work by enfant terrible Martin Creed, or a portrait of Oliver Cromwell almost cheek by jowl with one of Charles I, reinforces not just how far British art has come, but also how far we have politically too. To have the worlds of politics and art mingling so closely (the works are often broadly selected for their overarching suitability to a particular location) might displease some, but ultimately these are more than just diplomatic tools of the trade. They are essentially a snapshot of Britain through the ages, from a long-lost time when Britannia ruled the waves to its more uncertain place on the ever-changing world stage.