By polarized infrared absorption spectroscopy, we have determined the relation between the molecular orientation of a rubbed polyimide film and that of a very thin liquid crystal (LC) layer (approximately a monolayer of 8CB molecules) in contact with the polyimide film. The molecular orientation of the rubbed polyimide film was determined by fitting theoretically the incident angle dependence of the infrared absorption for molecular vibrations polarized parallel to the length of the polymer. Approximately a monolayer of 8CB molecules was deposited on a rubbed polyimide film with previously measured molecular orientation. The molecular orientation of this LC layer was also determined by polarized infrared absorption. We found that the LC molecules and the polyimide chains are oriented, on average, along the rubbing direction and tilted up from the surface, and that the molecular order of the LC layer is higher than that of the underlying rubbed polyimide film.