With Bu4NBr as phase-transfer agent, the monovacant polyoxometalates α-Xn+W11O（12-n）-39（X=P, Si, B, Ga） reacted in acetonitrile with electrophilic C6H5P（S）Cl2 to yield hybrid organic-inorganic species [C6H5P（S）]2XW11O（8-n）-39 in satisfactory yield, which have been characterized by elemental analyses, IR and 31P, 183W NMR. The formulation of all tetrabutylammonium salts of [C6H5P（S）]2·XW11（8-n）-O39 are in agreement with the results of elemental analyses, the hybrid anion consists of an α-Xn+W11O（12-n）-39 framework on which are grafted two C6H5P（S） groups through P\O\W bridges. The spectroscopic data show that the [PhP（S）]2XW11O（8-n）-39 compounds possess true Cs symmetry in acetonitrile and remain unsaturated.
