Abstract Methods for the synthesis of tetramethylbis (ω-phosphoryloxyalkyl) disiloxanes were developed. Thermal rearrangement of the 1, 2-shift type of tetramethylbis (phosphoryloxymethyl) disiloxanes was studied. The 1, 2-shift rearrangement of dimethyl ( diphenoxyphosphoryloxymethyl) silyl hydrogen sulfate was found.