The South China Sea (SCS) is characterized by abundant seamounts, which provide important information about the evolution of the SCS and related deep processes. Cenozoic volcanism in the SCS and its surroundings comprises three stages relative to the spreading of the SCS: pre-spreading (>32 Ma), syn-spreading (32-16 Ma), and post-spreading (<16 Ma). The pre-spreading magmatism predominantly occurs on the northern margin of the SCS and in South China coastal areas and shows a bi-modal affinity. The syn-spreading magmatic activity was very limited on the periphery of the SCS, but may be concentrated in the SCS. However, seafloor samples of this stage are not available yet because of overlying thick sedimentary deposits. Post-spreading magmatism is widespread in the central and southwest sub-basins of the SCS, Hainan Island, Leizhou Peninsula, Thailand, and Vietnam. These are mainly alkali basalts with subordinate tholeiites, and display OIB-type geochemical characteristics. The Dupal isotope anomaly and presence of high-magnesian olivine phenocrysts suggests their possible derivation from the Hainan mantle plume. The temporal and spatial distribution of Cenozoic volcanism in the SCS and its surroundings may be accounted for either by plate stress re-organization before and after SCS spreading, or by ridge suction of plume flow during opening of the SCS. If the latter is the case, the volcanic rocks within the SCS basin may not be typical mid-ocean ridge basalts (MORB). It remains puzzling, however, that the transition between the South China continental margin and the SCS basin does not have features typical of a volcanic rifted margin. Clearly, the relationship between mantle plume and SCS opening needs further evaluation. A better understanding of the link between deep processes and opening of the SCS not only requires enhanced studies on igneous petrogenesis, but also is heavily dependent on systematic sampling of seafloor rocks.