A novel initiator, i.e. trimethylsilylmethyllithium has been successfully used for the ring opening polymerization of cyclosiloxanes in toluene, in the presence of the cryptand [211]. Suitable conditions have been found in which monomodal distributions of molecular weights of polysiloxanes are observed by GPC, even in the case of D4 and 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl cyclotetra siloxane (D4Vi) polymerizations. Moreover, kinetics of propagation and of formation of cyclosiloxanes can be followed by Si-29 or C-13 NMR spectroscopy on living polymer solutions. The rate of propagation of hexaethylcyclotrisiloxane is 120 times lower than that of the corresponding dimethylated analog D3, under the same conditions.