A number of liquid crystal monomers based on methacrylate derivatives were synthesised by novel mild and solventless procedures under microwave irradiation. Their photo- and thermo assisted homo- and co-polymerizations with glycidyl methacrylate were investigated. The resulting polymers were characterised by NMR, GPC, DSC, and SEM to determine their structures and properties. The effects of the structures of the monomers on the electro-optical properties were correlated.