The modification of boron-doped amorphous hydrogenated silicon films [a-Si:H(B)] with femtosecond laser radiation is studied in this work. It is demonstrated that femtosecond laser crystallization of the a-Si:H(B) film area leads to extremely high values of the free charge carrier (hole) concentration, which is typical for degenerated semiconductors. The free charge carrier concentration is locally determined by measuring the Raman spectra in the modified areas. The shape of Raman spectra is typical for Fano resonance. It is found that the charge carrier concentration in the modified areas may exceed 1020 cm−3 depending on the femtosecond irradiation conditions. The areas with such a high concentration of free charge carriers are also characterized by high volume fraction of crystalline phase (more than 90%). Such a sharp increase in the free charge carrier concentration in the modified areas may be explained by an increase in concentration of electrically active boron atoms. The activation energy of the temperature dependence of the conductivity for laser beam treated areas is in full agreement with the data obtained from the analysis of the Raman scattering spectra.