A selection of paintings from the Art Collection include images of members of the Athenæum, artists, and poets, as well as a few presidential portraits. The portrait of George Washington is displayed in the Reading Room, while other paintings can be viewed in the Art Room and Philbrick Rare Book Room.

In 1796, Gilbert Stuart painted a portrait of George Washington for William Petty, first Marquis of Lansdowne, who helped shape the 1783 peace between the United States and Great Britain following the American Revolution. The Marquis also encouraged open trade between the two nations, which was negotiated in the Jay Treaty of 1796. The Lansdowne portrait, as this work became known, was painted during the treaty’s ratification, and Washington’s pen and inkwell likely refer to his signing of the document. While the painting specifically addresses the development of international trade, it more generally represents Washington's virtue and patriotism and became an admired and much-copied Washington portrait prototype. The copy of the Lansdowne portrait that hangs in the Providence Athenæum was painted by an unnamed "accomplished Italian artist," and was given by Samuel Larned (1788–1846), a Providence merchant and the Chargé d'Affaires to Chile and Peru. For someone as invested in trade and diplomacy as Larned, one can see why a portrait that celebrated the United States' international alliances would prove so compelling. Larned donated the portrait on the 1838 opening of the Benefit Street building, with the hope that its placement in the public halls of the library would encourage the virtuous and patriotic character of Providence’s youth.

Like many American artists of his generation, Newport-born portrait miniaturist Edward Greene Malbone knew his career would benefit from the imprimatur of Europe's cultural elite. With this in mind, he sailed in 1801 for London, where he worked for six months and attempted to make the acquaintance of England's leading painters. His efforts were rewarded by a resounding professional endorsement from no less than the President of the Royal Academy, Sir Benjamin West. After seeing one of his paintings, West declared that no English painter could excel Malbone’s skill. Malbone's The Hours, completed during his stay in London, may well have been the work that West so admired. The three female figures represent the Greek horae, goddesses that personify the orderly passage of time. That a portraitist such as Malbone should have portrayed a mythological scene suggests a desire to impress his colleagues in London, where historical and mythological subjects were especially valued. Malbone never sold the work and, following his early death from tuberculosis in 1807, it descended to his sister, Harriet Whitehorne. Whitehorne hoped to sell the miniature to the Providence Athenæum in 1846, but her asking price of $1200 was prohibitively expensive. It was not until 1854 that the library was able to acquire The Hours, using funds raised by Eliza Patten, the teenage daughter of the Athenæum’s Vice-President.

One of the Athenaeum’s finest paintings, The Girl Reading is attributed to Sir Joshua Reynolds The portrait is said to be of Reynolds’s favorite niece, Theophila Palmer, and was exhibited at the Royal Academy in London in 1771. Horace Walpole visited the exhibition and wrote in his catalog that the portrait was “charming.”

Although Sarah Helen Whitman is most commonly known for her courtship with Edgar Allan Poe, conducted among the stacks of the Providence Athenæum in 1848, she was also an important cultural figure in her own right. A poet herself, she was closely affiliated with prominent authors in Boston and New York, and a hostess of literary salons in Providence. This work was painted by artist Cephas Giovanni Thompson, perhaps best known for his portrait of Nathaniel Hawthorne, and shows Whitman in the mourning cap she wore after the 1833 death of her husband, John Winslow Whitman. Although the cap recognizes her widowhood, its flowing pink streamers are unconventional and speak to Whitman’s gentle disavowal of social norms. A 1923 essay on Poe and Whitman offers a persuasive interpretation of the painting as portraying Whitman’s charm, forceful intellect, and nonconformist tendencies, referring to her pink ribbons as "the dainty rebel's badge."

The painting is by James Sullivan Lincoln of Providence, a long-time acquaintance and friend of Bartlett and a noted nineteenth-century portrait artist. Bartlett was a founder of the 1831 Providence Athenæum located in the Providence Arcade, and instrumental in the governance of the institution and acquisition of important collections including the Description de l’Egypte. In 1914 several years after his death, part of his personal library was donated to the Athenæum by his heirs.