The optical properties of the thin films of asymmetrically substituted polysilane homopolymers and copolymers were studied. A conformational change in the organopolysilanes having (pentoxy,methyl) or (hexyl,methyl) groups was observed by polarized UV spectrometry and a wide angle X-ray diffraction. The polysilanes and polysilane copolymers having hexyl and pentoxy side chains were crystallized to form oriented films along the direction of the mechanically oriented polytetrafluoroethylene (PTFE) films. The bathochromic shifts were observed for polysilane and the polysilane copolymer having pentoxy side chains when the film thickness was small (ca. < 50 nm). The influence of the thickness of the films on the spectral change was significant when the substituent was a pentoxy group, however, not when it was a hexyl group. (C) 2003 Elsevier Ltd. All rights reserved.