Mixed films containing poly(dihexylsilane) (PDHS) and liquid crystal (LC) molecule were prepared onto a rubbed poly(vinyl alcohol) film by spin-casting. The conformational state and the alignment of the PDHS backbone were investigated by polarized UV-visible absorption spectroscopy. The absorption band ascribed to the crystalline state of PDHS in the mixed film showed a red shift from that of a pure PDHS film. The PDHS backbone in the mixed film was aligned parallel to the rubbing direction. The magnitude of the red shift and the alignment order of PDHS was enhanced by annealing at 60 degreesC in the mixed film with some LC molecules.