We synthesized a series of polystyrene derivatives containing various side chain terminal moieties, such as phenoxymethyl, 4-methoxyphenoxymethyl, 4-fluorophenoxymethyl, 4-methylphenoxymethyl, and 4-trifluoromethoxyphenoxymethyl groups, using polymer analogous reactions, in order to investigate the effect of the side group on their liquid crystal (LC) alignment behaviors. The polymers containing 4-fluorophenoxymethyl, 4-methylphenoxymethyl, or 4-trifluoromethoxyphenoxymethyl side groups had lower surface energy values and the LC cells fabricated using the unrubbed films of these polymers showed homeotropic LC alignment behavior. The LC cells fabricated using the rubbed films of the polymers containing phenoxymethyl or 4-fluorophenoxymethyl groups showed homogeneous planar LC alignment behavior in which the LCs were aligned perpendicular to the rubbing direction. This homogeneous planar and perpendicular alignment behavior was ascribed to the favorable anisotropic interactions between the LC molecules and the side groups preferentially oriented perpendicular to the rubbing direction.