The present invention relates to a siloxane monomer containing a trifluorovinylether group and a sol-gel hybrid polymer prepared using the monomer, more particularly to siloxane monomer with novel structure prepared by reacting alkoxychlorosilane with a Grignard reagent containing a trifluorovinylether (--OC.sub.2F.sub.3) group, a method of preparing the same and a sol-gel hybrid polymer containing a perfluorocyclobutane (PFCB) group prepared from sol-gel reaction using said siloxane monomer containing a trifluorovinylether group.