The library has a rich collection that covers all areas of Latin America It is one of the largest libraries in South America, and an important source of growth was the enactment of the 1825 Law of Delivery, which required the delivery of 15 volumes of every kind of book or pamphlet published in Chile. In addition to preserving Chilean literature, the National Library is also a depository of Chilean federal government publications.

In 1877, the National Library published the important In 1877, the National Library published an important national bibliography, the Annals of Chilean Publications, which was renamed the Biblioteca de Chile in 1976. The National Library used the NOTIS system in the 1980s, using machine-readable catalog tapes, and the program was designed to include the collections of the University of Chile in addition to those of the National Library. The program was designed to include the collections of the University of Chile in addition to the National Collection. Because of the emphasis on automation, the library is well informed.

Number of collections: 1.6 million volumes, 942 titles, 83 volumes of cradles, 40 degrees, 6,373 pieces of sheet music, 10,331 maps, 20,000 microfilms, 5,500 16/35 film reels, 300 audiovisual materials, 2,013 sound recordings, 36 CD-ROMs, and 1,000 CD-ROMs. The company has 36 CD-ROMs, 110,000 documents, and 115 videotapes.