Historical-artistic's collection meets the most ancient pieces today retains the Biblioteca Nacional, linked to its origins as Royal Library Service (1711): among them, the portrait of Felipe V and his family signed by Miguel Jacinto Meléndez or objects such as large mathematical instruments of Carlos II which consists in the first inventory of the library of the Torre del Alcazar stone fortification.

In the late nineteenth century and early decades of the twentieth century, it opens up a second time artistic collections of the library, pointed out by two key milestones: firstly, for creating the Archaeological museum in 1867 from the collections of former Museum of antiquities of the library and, secondly, because of its installation in 1896 in its current headquarters in a common building then with other museums and institutions: the National Libraries and museums. These years corresponds most of the historic furniture, as well as portraits of librarians, directors of the Library or writers such as José Espronceda, josé Zorrilla, Juan E. Hartzenbusch, Manuel Tamayo and Baus or Marcelino Menéndez Pelayo. Signed by authors such as Ignacio Suárez Llanos, Antonio Maria Esquivel or José and Federico of Madrazo, some give effect to a provision of the rules of procedure of the library of 1875, by which It would make into its mandate to collect a collection of portraits of the spanish literati. Another important series of paintings of this period is the Don Quijote undertaken and donated by Antonio Muñoz Degrain to decorate the Room Cervantes (1920).

At the end of the twentieth century date back to other bodies, such as the portraits of awarded the Cervantes who, by provision of the ministry of culture are responsible every year since 1999.

Furniture, sculptures, musical instruments, music equipment mechanics, typewriters and industrial equipment related to the arts of the book, both with the binding as typography subjects and engraving make up the whole of this collection, marked by a heterogeneous character, also testimony to the evolution of the institution over the more than 300 years of history.