Organophosphoryl polyoxotungstate derivatives α-[PhP(Y)]2Xn+W11 [image omitted] (Xn+ = Ge4+, B3+; Y = O, S) have been obtained by the reaction of the monovacant α-[Xn+W11O39](12-n)- (Xn+ = Ge4+, B3+) anions with PhP(O)Cl2 or PhP(S)Cl2 in acetonitrile. These new organic-inorganic hybrid anions have been characterized by elemental analysis, IR, 31P and 183W NMR spectroscopy. According to the elemental analysis and spectroscopic data, the hybrid anions consist of an α-[XW11O39] framework on which are grafted two equivalent PhP(O) or PhP(S) groups through P-O-W bridges. The six-line 183W NMR spectrum indicates that the hybrid anions possess Cs symmetry in acetonitrile.