The present invention relates to an initiation system composed of the reaction product of at least one cyclic siloxane and at least one organometalic compound of sufficient reactivity to open the siloxane ring. Application of the present invention is to the preparation of homopolymers of (meth)acrylic, vinylaromatic or diene monomers, random or block copolymers of these monomers and, in particular, application to poly(methylmethacrylate) with a high content of isotactic triads.