The orientation-induced conformational transition was studied on thin films of poly(methylhexylsilane) (PMHS). The orientation behavior of molecular chains was analyzed by the inclination-angle-dependence of the polarized UV spectrum and the FTIR reflection-absorption spectroscopy (RAS). The changes in conformation of PMHS chains were monitored with the UV absorption spectrum. It was shown that the structure of the spin-cast film depended upon the thickness of films. In thick film (408 nm), molecular chains are not oriented, and favor the disordered conformation, which shows absorption band at 300 nm. In contrast, extended conformation with trans-rich segments is produced in addition to the disordered conformation in thin spin-cast films (45-100 nm). The extended conformation gives rise to a sharp absorption band at 338 nm. The molecular chains with extended conformation are oriented parallel to the substrate surface. The uniaxially oriented films were prepared by drawing the him on supporting polymeric substrates and by crystallization on highly oriented polymer films. As the degree of orientation is increased, the 338 nm band increases in intensity relative to the 300 nm band. The 338 nm band dominated the UV spectrum of the highly oriented PMHS him instead of the 300 nm band. A conformational transition to the extended conformation from disordered state is induced by the molecular orientation, exhibiting a drastic spectral change in the UV spectrum.