Induction mechanism of molecular orientations for a rubbed polymer film as an alignment layer was investigated using polarized UV/Vis spectroscopic experiments for polyimide and polyvinylcinnamate whose conjugated electrons are located along main chain and side chain, respectively. By determining anisotropy formed in the rubbed film, LC director formed in the LC cell, and orientation direction of deposited pentacene molecules, it was found that LC orientation was induced mainly by molecular interactions whereas surface microgrooves formed by the rubbing process affect the orientation direction of deposited pentacene molecules.