Surface molecular orientation and relaxation of aromatic polyimide liquid crystalline containing pendent cyanobiphenyl mesogens in thin films were investigated by surface-enhanced Raman scattering (SERS) using silver particles as overcoating layer which was chemically deposited from a solution. SERS measurements for samples of current interest, such as ultrathin polyimide film, were successfully performed without disturbing the surface morphology. The results of this work show that our SERS sampling technique is particularly effective for surface study on polymer films.