Base-stabilized silanone complex Cp*(OC)2W(SiMe3){OSiMes2(DMAP)} (2) was synthesized by the reaction of (silyl)(silylene)tungsten complex Cp*(OC)2W(SiMe3)(SiMes2) (1) with 1 equiv of pyridine-N-oxide (PNO) in the presence of 4-(dimethylamino)pyridine (DMAP). Further oxygenation of 2 with 3 equiv of PNO at 80 °C resulted in the formation of a W–O–Si–O–Si framework to give disiloxanoxy complex Cp*(O)2W{OSiMes2(OSiMe3)} (3). Complex 3 was also obtained by the direct reaction of complex 1 with 4 equiv of PNO at 80 °C.