A new geochronological and geochemical study of the volcanic rocks of the Ponza and Palmarola Islands, Pontine Archipelago, has been carried out. This archipelago is located along the boundary between the Italian continental shelf and the opening Tyrrhenian basin. It is a key area to study volcanism related to the opening of the Tyrrhenian Sea. Ponza is the oldest felsic magmatic manifestation in the central Tyrrhenian area. Previous studies suggested that Ponza volcanic activity began before 5 Ma. Twenty-five new K–Ar ages constrain the volcanic activity (rhyolitic hyaloclastites and dykes) to the last 4.2 Ma, with two episodes of quiescence between 3.7 and 3.2 Ma and between 2.9 and 1.0 Ma. A new volcanic episode dated at 3.2–2.9 Ma has been identified on the central and southern Ponza, with emplacement of pyroclastic units. At 1.0 Ma, a trachytic episode ended the volcanic activity. The near island of Palmarola exhibits rhyolitic hyaloclastites and domes dated between 1.6 and 1.5 Ma, indicating that the island was entirely built during the Early Pleistocene in a short span of time of ca. 120 ka. Although only 6–8 km apart, the two islands display significantly different geochemical signatures. Ponza rhyolites show major and trace element compositions representative of orogenic magmas of subduction/collision zones: high-K calc-alkaline and metaluminous rhyolites (Agpaitic Index [AI] and Alumina Saturation Index [ASI] <1), high LILE/HFSE (Th/Ta=16–21) and LREE/HFSE ratios (La/Nb>3), and Nb–Ta negative anomalies. In Palmarola, the orogenic character is also present, but much less marked than in Ponza: rhyolites have a peralkaline character (AI>1), lower LILE/HFSE (Th/Ta=11–15), low LREE/HFSE ratios (La/Nb=1–2) close to those of anorogenic lavas, and the Nb–Ta negative anomalies are almost absent. Y/Nb ratios indicate different magmatic sources, one similar to island-arc or active continental margin basalts for Ponza rhyolites, and the others probably involving an OIB type component for Palmarola rhyolites and Ponza trachytes. Palmarola volcanics represent a transitional magmatism: although a preserved collisional geochemical imprint, they show geochemical features approaching those of anorogenic lavas erupted in a within-plate context. The change of magmatism evidenced in this study can be related to the tectonic evolution of the area. Indeed, Hf, Ta and Rb contents suggest that the oldest Pliocene rhyolites of Ponza would emplace in a syn- to late-collisional setting, while the younger Pleistocene rhyolites of Palmarola would be emplaced in a post-collisional setting in which the orogenic character (Th/Ta) decreases and mantle influence (Nb/Ta) increases. Geochemical modeling strongly suggests that the Palmarola rhyolites represent the waning stages of a subduction-related magmatism. The K–Ar datings allow us to estimate precisely the transition of magmatism to last less than 1.3 Ma. The transitional magmas may be the result of the upwelling of asthenospheric mantle inducing melting of a metasomatized lithospheric mantle and the mixing between these two sources. This upwelling could occur during the extension of the Tyrrhenian basin, caused by the slab retreat and steepening, or during a process of slab break-off starting in the Pliocene.