Phenylene-containing monomer 1 possessing O-methacryloyl and styrene double bonds with different reactivities in radical polymerization was designed as new type of bifunctional monomers suitable for preparation of LC photoaligning alkene-functionalized polymers. To elucidate an individual contribution of double bond of each type into kinetics of bifunctional monomers polymerization, thermo- and photo-induced polymerization of model monomers were investigated and compared. Polymer poly-1 obtained by thermo-induced radical polymerization demonstrated high efficiency of LC ZLI 2293 photoalignment.