A novel series of poly(2-chloroethyl glycidyl ether)-based side-chain liquid-crystalline copolymers has been synthesized in which the mesogenic units are biphenyl 4-methoxybiphenyl, 4-methoxyazobenzene, and N-benzylidene-4-methoxyaniline, respectively (corresponding polymers are referred to as PCBH, PCMB, PCMA, and PCBM). The structures of the compounds obtained are characterized by infrared (IR) and 1 H nuclear magnetic resonance (NMR). The thermal properties were investigated using polarized optical microscopy, differential scanning calorimetry, and X-ray diffraction analysis. The results indicate that PCMA, PCMB, and PCBM exhibit thermotropic liquid-crystalline behavior and present nematic phases with Schlieren textures. However, PCBH does not display a mesogenic phase. The decomposition temperatures of copolymers begin at 290 C.