The National Library of Wales is based in Aberystwyth, overlooking the Ceredigion Coast. The Library was granted a Royal Charter in 1907 with a clear mandate to develop a hybrid collection with artworks as part of an overall strategy to preserve a large range of printed and original material.

The paintings collection is focused around Welsh subject matter, Welsh portraits and Welsh artists. From the start, the emphasis was to create a collection of works that represented specifically the place of Wales and the Welsh nation within history and the world. It is rich and varied. Two highlights of the early collection are the portraits 'Thomas Charles of Bala (1755–1814)' by William Roos, gifted by the artist Buddig Pughe, and Brenda Chamberlain’s 'Peter Kahn'.

Later additions include the magnificent bequests of Sir Kyffin Williams and Donald McIntyre. Single gems are: 'Dolbadarn Castle' by J. M. W. Turner, the portrait of Dr Richard Price by Benjamin West, and 'Dewi yn Llanddewi Brefi (c.500–581)' by Evan Walters.