The original collection comprised about 8200 volumes (7200 titles), almost entirely in Portuguese. Subsequently, a number of duplicates were discarded and the present collection contains about 870 volumes in the Rare Books Collection and about 6000 volumes in the general collection.

The main strengths of the collection are literature, history and religion, and there are also works on politics, topography, archaeology, art, Portuguese exploration, Portuguese colonies, heraldry, genealogy, language and bibliography.

Literary works total about 2000, of which about half consist of plays, mostly published in the eighteenth and nineteenth centuries. Among the notable Portuguese writers represented in the collection are Jose Valentim Fiahlo de Almeida, Joao Almeida Garrett, Alberto Braga, Teofilo Braga, D. Joao da Camara, Camilo Castello Branco, Raul Brandäo, Luis de Camoes, Ferreira de Castro, Luis Chaves, Sousa Costa, Julio Dantas, Antero de Figueiredo, Joao Grave, Alexandre Herculano, Marcellino Mesquita, Jose Carlos dos Santos and Alberto de Sousa Costa.

Some of the more substantial works in the collection include:

• Agostino, José, Historia da literature portuguesa (1927)
• Barboso Machado, Diogo, Bibliotheca luzitana escolhida (1786)
• Bluteau, D. Raphael, Vocabulario portuguez e latino (10 vols, 1712–21)
• Carvalho da Costa, Antonio, Corografia portugueza, e description topografica reyno de Portugal (3 vols, 1706–12)
• Corpus juris civilis (2 vols, 1759)
• Figueiredo, Manuel de, Theatro (15 vols, 1804–10)
• Latino Coelho, Jose Maria, Historia politica e military de Portugal, desde os fins do XVIII seculo ate 1814 (3 vols, 1874–91)
• Machado, Elza Paxero, and Machado, José Pedros, (eds), Cancioneiro da biblioteca nacional, antigo Colocci–Broncuti (8 vols, 1949– )
• Rebello da Costa, Agostinho, Descripcao topografica, e historica da cidade do Porto (1789).

There are a large number of periodicals in the collection. Some of the longer runs are:

• Almanach de Lisboa (1786–1823)
• Almanach dos palcos e salas (1905–17)
• Annuario da Camera dos senhores Deputados (1883–1907)
• Annuario do Gremio Artistico (1890–98)
• Arqueologia e historia (1922–32)
• Boletim dos Museus Nacionais de Arte Antiga (1939–43
• Investigador portuguez em Inglaterra (1812–17)
• O Espectro (1846–47)
• O Recreio (1885–99)
• Terra portuguesa (1916–27).

The Valente Collection contains 40 manuscripts and typescripts, including a number of plays and also poetry, music and historical and religious works. They mostly date from the nineteenth century. The only modern work is a three-volume typescript history of Coimbra University in the period 1834–85, written in 1960.

The Valente Collection was purchased by the Library in 1970 from Livraria Histórica e Ultramarino of Lisbon.

The periodicals in the Valente Collection have been integrated in the general collection, while the books have been kept together as a formed collection. About 590 titles (870 volumes), consisting of pre-1801 imprints and modern works of considerable aesthetic value, are held in the Rare Books Collection. The remainder of the books are in the general collection. The call numbers have the prefix RB VAL and VAL.

The manuscripts are held in the Manuscripts Collection. They have been catalogued at the collection level, but there is no listing.