The molecular orientations of thermally imprinted polyimide (PI) films with different film thickness were investigated by the polarized Fourier-transform infrared spectroscopy (P-FTIR). The results illustrated the molecular orientation in the residual layers and the one in the higher-lines were different. The polymer main chains in the residual layers were perpendicular to the lines and parallel to the substrate. The polymer main chains in the higher-lines were aligned normal to the substrate and C=O bonds perpendicular to the main chain were aligned along the line direction. The orientation of liquid crystals on the alignment layer was investigated by atomic force microscopy (AFM) and polarized optical microscopy (POM). The results demonstrated imprinted PI film could be an alignment layer for liquid crystals. (C) 2015 Elsevier Ltd. All rights reserved.