Diogo Homem's A Chart of the Mediterranean Sea, 1570, is over a metre wide
More than simply a topological survey of a country or continent, the maps on display are as diverse as their decorative features - from hunting dogs to sea monsters and cherubs blowing the winds across the ocean.
Picked from a "long shortlist" of 26,000 maps from the library's 4.5 million-strong collection, curators Peter Barber and Tom Harper carefully selected 80 impressive wall maps, some of which have never been displayed in public.
The artistry of maps is seductive and like the teaspoon of sugar that helps the medicine go down
The maps on show date from 200AD to the present day. Some are made of silver, carved in wood or marble, or stitched tapestries that were intended for display side-by-side with some of the world's greatest paintings and sculptures.
Some of these "pictorial encyclopaedias" rival them in their artistry.
Diogo Homem's 1570 Chart of the Mediterranean sea is dripping with gold and saturated colour, while Pierre Descelier's World Map of 1550 is a hand-painted visual representation of the legends and natural history of the world.
Fred W Rose's war map depicts Russian foreign policy as the tentacles of an octopus threatening and throttling the Ottoman Empire.
Aside from the aesthetic quality, this artistry and creativity by the cartographers do serve a purpose, Mr Barber explains.
"The main purpose of virtually all of the maps here is propaganda because propaganda consolidates power.
"But the power isn't necessarily political, it could be for status, such as the map of a merchant's estate. And for a map has to be pretty to work as a status symbol. An ordinary ordnance survey map would not do.
"The artistry of maps is seductive and like the teaspoon of sugar that helps the medicine go down, tries to persuade us to swallow a particular political message."
The world's smallest atlas, made for doll's house of Queen Mary, is on show
When geography came into being as a subject during the Enlightenment maps have been regarded as its handmaiden.
Art, they argue, has no place.
"Since about 1800 people have tended to associate maps with mathematical geography, but it is a self-closing view to say if something is pretty it can't be a map," says Mr Barber.
"Lots of people consider it superficial and wrong for us to include these decorative maps in the exhibition. In some cases they don't appreciate art and at a deeper level there is still the view that if a map is not primarily about geography and measurement then it really shouldn't be included.
"But some of the outstanding examples in this exhibition have actually been acquired in art galleries rather than from map dealers, such as Grayson Perry's Map of Nowhere and Steven Walter's London.
"We have also acquired political posters containing maps, some of which are quite striking images that have only recently become available from map dealers.
"With this exhibition I wanted to talk to my peers and show them that maps were works of art and demonstrate that they played a role in court life, in political life.
"Sometimes when you make this point some people look at you like you're a man from Mars."
Meanwhile, a new exhibition examining the crossover between art and geography is to open at the Royal Geographical Society (RGS).
The RGS asked contemporary artists Susan Stockwell and Agnes Poitevin-Navarre to respond to their extensive collection of maps.
Creative Compass examine themes of migration, identity, gender and global economics inspired by the maps and photographs.
Stockwell has produced several pieces inspired by maps
Stockwell, meanwhile, raises questions about the global economics of power and colonial histories in her series of "money maps" and an intricate Victorian dress.
The dress is made from a map of the world with the countries and continents carefully placed to relate to an organ of the human body.
Her map of Afghanistan, made from US dollars carefully stitched together, is a subtle comment on American imperialism. The red stitching closely echoes US state lines.
Maps are an important theme running through Stockwell's work - a map of the world made out of Chinese currency hangs at the V&A Quilts show - and it is an area she admits to be "fascinated" by.
She said: "Maps have this geo-political content. They are also about power and war and gaining territory, and, as an artist, I'm fascinated by them.
"I realised mapping is a very male language, a very particular male world that is very powerful in its own way. So by making a dress out of maps, which is about power and ownership and possession, is subverting the material and getting people to look at it differently.