The synthesis and the thermotropic behavior of new monomers and side-chain liquid-crystalline polymers were studied. For the functionalization of the methacrylic and acrylic monomers, a bromine end-functionalized dialkoxyterphenylene, showing both liquid-crystalline and light emission properties, was used. Monomers were polymerized by AIBN-initiated and thermal polymerizations. The thermotropic behavior of compounds was studied by DSC, POM and XRD. Results indicate a well-defined thermotropism, which was attested by the multiple thermal transitions and different optical textures. X-ray diffraction patterns showed several equidistant sharp reflections at low angles following monolayer and bilayer structures of tilted smectic phases for the monomers and polymers, respectively.