The mechanism of excess electron and hole localizations in radical ions of poly(dimethylsilane) (PDMS) has been investigated by means of molecular dynamics (MD) and extended Hückel methods. Oligo(dimethylsilane) composed of 100 monomer units of dimethylsilane, CH3(Si(CH3)2)(n)CH3 (n = 100), were used as a model of PDMS. Both wings of the oligomer were capped by a methyl group. First, the geometry of PDMS with a regular all-trans form was fully optimized by MM2+ energy gradient method. Next, the MD calculation was carried out for PDMS at 300 K. The structure of PDMS was gradually deformed as a function of simulation time, especially the dihedral angle of Si-Si-Si-Si backbone that was randomized. At time zero when the structure has the regular all-trans form, both the excess electron and hole were completely delocalized on the Si backbone of PDMS. After thermal activation, the localization of the electron and hole was found. The mechanism of the localization was discussed on the basis of theoretical results.