Polymorphous silicon (pm-Si:H) films have been prepared by a new regime of plasma enhanced chemical vapour deposition in the region adjacent of phase transition from amorphous to microcrystalline state. Comparing to the conventional amorphous silicon (a-Si:H), the pm-Si:H has higher photoconductivity (sigma(ph)), better stability, and a broader light spectral response range in the longer wavelength range. It can be found from Raman spectra that there is a notable improvement in the medium range order. There are a blue shift for the stretching mode of IR spectra and a red shift for the wagging mode. The shifts are attributed to the variation of the microstructure. By using pm-Si:H film as intrinsic layer, a p-i-n junction solar cell was prepared with the initial efficiency of 8.51% and a stabilized efficiency of 8.01% (AM1.5, 100mw/cm(2)) at room temperature (T(R)).