Mesogenic monomers of 4-[6-(acryloyloxy) hexoxy] benzoic acid (AHB) and 4-[[6-[(2-methyl-l-oxo-2-propenyl)oxy]hexyl]oxy]-benzoic acid 4′-[(1-oxo-10,12-nonadecadiynyl)-oxy]-[1,1′-bi-phenyl]-4-yl] ester (MHNB) are prepared for polymerization in highly ordered smectic and nematic mesophases and liquid crystal solvents. AHB exhibits smectic C and nematic mesophases, whereas MHNB displays the phase sequence of smectic X, C, A and nematic phases. The highest molecular-weight polymers with the widest molecular-weight distribution were found in polymerization of the highly ordered smectic phase and using smectic solvents. Photopolymerization in nematic systems gave the narrowest molecular weight distribution polymers when compared with those in other systems.