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 1H 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.