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The original core of the palace dates back to the middle of the 16th century, as the residence of the Jacobbili family. In 1583 it was sold, still unfinished, to the Rucellai family, who commissioned Bartolomeo Ammannati (1511-1592) to complete the building.
The Florentine architect extended the façade onto Via del Corso and built a beautiful loggia overlooking the garden. The palace gallery was frescoed in these years by Jacopo Zucchi and enriched with a collection of antique sculptures. In 1629 it was purchased by the Caetani family, who in the following year commissioned Bartolomeo Breccioli to modify the façade overlooking Largo Goldoni, adding windows to the right of the 16th-century ashlar portal and abolishing the mezzanine, which was transformed into a second floor. Around 1640 Martino Longhi the Younger (1602-1656) built the majestic staircase rising from the portico to the loggia overlooking the inner courtyard, considered one of the four wonders of Rome, and the belvedere tower above the roof. In 1776 the building passed to the Ruspoli family, who are still part owners today. The palace has wide three-storey facades with architraved windows on the first floor, triangular gables on the second and a simple cornice on the third; the corners have rusticated edges.
In the first half of the 19th century, the ground floor housed the "Caffè Nuovo", the city's most elegant café.
Among the illustrious guests of the palace was Napoleon III.