A series of photoreactive mesogens based on chalcone were prepared and their morphological behavior and reactivity were studied according to a variable number of alkyloxy tail carbons. The linear ester compounds 3a-h comprised two chalcone units connected to a benzene ring through ester linkages. All linear ester compounds showed enantiotropic liquid crystalline phases. The X-ray diffractograms for the mesophases of compounds 3a-h showed a set of reflections in the small-angle region which consisted of more than three sharp diffraction peaks with d spacings in the ratio of 1:1/2:1/3, confirming the well defined smectic A structures of the compounds. Compounds 3a-h were considered to be bifunctional monomers due to the presence of two photoreactive chalcone groups. Upon UV irradiation, its polymerization proceeded through the [2+2] addition reaction between chalcone units in a stepwise manner. An image pattern was obtained by the photopolymerization of the liquid crystal of the compound (3h) with decyloxy tails through a photomask. The irradiated part became dark while the masked part remained birefringent under polarized optical microscopy, which was ascribed to the production via the UV irradiation of a polymer or a dimer having cyclobutane rings by [2+2] addition, which thereby disrupted the alignment of the molecules.