The ESR, ESSEM and spectrophotometric studies on polysilane radical ions revealed that charge carries, hole and conducting electrons, are not delocalized all over the Si-Si main chain but confined to a part of the chain composed of only six Si atoms, probably near the branch on the main chain. Comparison of the ESR spectra of the radical cations and anions revealed that the hole can migrate from a main to an adjacent chain via the side chains, whereas the conducting electron can not migrate since the side chains act as good intermolecular insulators for the electron.