A novel initiator, i.e. trimethylsilylmethyllithium has been successfully used for the ring opening polymerization of cyclosiloxanes, in toluene or in the bulk, in the presence of the cryptand [211] or DMSO. Suitable conditions have been found in which monomodal distributions of molecular weights are observed for homopolymers of 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane (V-4) as well as for copolymers of V-4 with D-3 or D-4.