The routes of synthesis, as well as, spectroscopic and X-ray diffraction characterization of a new group of bis- or hexakis-4-(dimethyl(vinyl)silyl)phenoxy and 4-(dimethylsilyl)phenoxy-substituted cyclotriphosphazenes as a versatile starting substrates for the synthesis of a variety of organic cyclophosphazene derivatives, via catalytic hydrosilylation or silylative coupling processes, is presented