We designed and synthesized new smectic liquid crystalline monomers containing photopolymerizable acrylate groups and a mesogenic core unit composed of two benzene rings, one pyrimidine-based heteroaromatic ring and an acetylene linking group. The structures of monomers were characterized by 1H nuclear magnetic resonance spectroscopy, and their mesomorphic behaviors were investigated by differential scanning calorimetry and polarized optical microscopy. Both of monomers showed an enantiotropic phase transition behavior with exhibiting both nematic phase and highly ordered smectic phase. Both of monomers showed smectic phases during the cooling process in the temperature range of 144.2-94.0 °C and 154.0-85.8 °C, respectively. Neither of these compounds showed a homogeneous alignment even at various temperatures, and therefore, their 50:50 mixture was chosen for the preparation of guest-host mixture because of its lowest crystallization point, wide smectic phase temperature range and superior aligning property. Polymerizable “host-guest” mixture formulated from the host liquid crystalline monomer mixture, dichroic dye and additives was injected into the sandwiched glass substrates having rubbed alignment layers at the isotropic temperature. Subsequent in-situ photopolymerization by UV irradiation at room temperature successfully resulted in a thin film polarizer with good polarizing properties. The fabricated guest-host polarizer showed a dichroic ratio (DR) of 13.1 and a degree of polarization (DOP) of 95.5% with the thickness of 5 μm.