In this research, we report the preparation of doped PMo Keggin heteropolyacids where Mo is partially replaced by V, Bi, and Bi–V. These catalysts were characterized by means of ICP-AES analysis, 31P-NMR, UV–visible spectra, FT-IR spectra, thermal analysis, and textural properties. In addition, the activities of the synthesized catalysts were evaluated in the selective oxidation of sulfides to sulfoxides/sulfones. The incorporation of V, Bi and Bi–V into the structure of H3PMo12O40 increases the catalytic activity. The two most active catalysts, those with V and V–Bi were supported on aminopropyl-functionalized silica (SiO2NH2) and they were found to be and efficient heterogeneous catalysts for the selective oxidation of diphenylsulfide to the corresponding sulfoxide/sulfone.