Alignment direction of liquid crystals (LCs) on a rubbed polymer surface is related to a slow axis of polymer surface. Some LCs, however, have been reported to align perpendicular to the slow axis on the rubbed polymer surface. In this study, LCs with negative dielectric anisotropy which align perpendicular to the slow axis and LCs without a polar function group which align parallel to the slow axis are mixed and the alignment direction of mixtures are investigated on rubbed polyvinyl imidazole (PVIz) and poly(4-vinyl pyridine) surface. A separation of the alignment which might be caused by a selective adsorption of the LC on the PVIz surface was observed when the LC mixture using negative types of LC with CN groups was injected in the isotropic phase.