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Organopolysilanes are expected to be used for future optical and electronic devices. Poly(di-methyl silane), [Si(CH3)2]n, the most fundamental organopolysilane, is not solved in organic solvent at room temperature. Therefore, we have proposed the vacuum evaporation technique in order to obtain thin films of poly(di-methyl silane). In this paper, optical and electrical properties of poly(di-methyl silane) thin films are examined. As a result, it is found that the electric conductivity parallel to the Si backbone is larger by about three orders of magnitude than that perpendicular to the Si backbone. Moreover, highly oriented poly(di-methyl silane) thin film prepared by the vacuum evaporation technique is applied to the dye-sensitized solar cell, and we have succeeded in fabricating the perfectly solid-state dye-sensitized solar cell using poly(di-methyl silane) thin film.