This work presents the first synthesis of a new polymer obtained by catalytic addition of the Si-H groups of a poly[methyl(H)silane-co-methylphenylsilane] backbone to N-(allyl)cycloimmonium salt. This hybrid polymer was characterized by the spectroscopic analysis, thermogravimetric analysis and gel-permeation chromotography (GPC). The pendant N-(allyl)cycloimmonium segments lead to the formation of molecular dipoles, as evidenced by electrical polarization experiments.