The primary correspondence (ca. 65 letters) is with William Cooper (1798-1864) on Bonaparte's publications, especially "American Ornithology" and "Observations on the Nomenclature of Wilson's Ornithology," but also included are many references to American and European men of science and learned societies. There are also letters to Isidore Geoffroy Saint-Hilaire, George Robert Gray, Titian Ramsay Peale, and Wilhelm P. S. Rüppell.

This collection contains miscellaneous letters and papers relating to explorations of South America, Cuba, and Mexico; scientific investigations; Latin American antiquities and linguistics; and publications. There are also copies of 26 letters from Humboldt to Pierre Hyacinth Azais and Jules Berger de Xivrey, from originals at the Duke University Medical Center Library.

The Peale family is best known as a family of artists; however, family interests and activities were much more wide-ranging. The best known Peale is Charles Willson Peale (1741-1827, APS 1786), who produced more than one thousand paintings, including hundreds of portraits of leading Americans during the colonial and early national periods. Peale was married three times, to Rachel Brewster (1744-1790), Elizabeth de Peyster (1765-1804), and Hannah More (1755-1821). He had eighteen children, eleven of whom reached adulthood. Three of Charles Willson Peale's sons became artists: Raphaelle Peale (1774-1825), Rembrandt Peale (1778-1860), and Rubens Peale (1784-1865). A fourth son, Titian Ramsay Peale (1799-1885, APS 1833), was a naturalist (who made drawings on the exploring expeditions he accompanied) and pioneer in photography, and another son, Benjamin Franklin Peale (1795-1870), became a naturalist and paleontologist. Peale's daughter Sophonisba Angusciola was married to Coleman Sellers (1781-1834), an inventor and manufacturer of machinery, including locomotives. Two of their sons, George Escol Sellers (1808-1899) and Coleman Sellers (1827-1907, APS 1872), were inventors and engineers. The latter served as director of the construction of the hydro-electric power development at Niagara Falls. He was married to Cornelia Wells Sellers (1831-1909). One of their grandsons was Charles Coleman Sellers (1903-1980, APS 1979), a librarian and historian and the author of several studies of the Peale family, including a Charles Willson Peale biography.