Doubly-oriented films of poly-(di-methyl-silane) (PDMS) were prepared by evaporation under controlled conditions on unidirectionally oriented poly(tetra-fluoro-ethylene) (PTFE) thin layer, which was mechanically deposited on fused quartz plate. It was confirmed by X-ray diffraction and polarized absorption measurements that the silicon backbone chains with all-trans conformation laid along the direction of PTFE orientation, and that a particular crystalline plane (110) was parallel to the PTFE layer. PDMS films with double orientation showed a new absorption which appeared only in the polarized spectrum parallel to the direction of chains, and in lower energy region, than the main peak at 4.1 eV.