Hole carrier densities and Raman spectra were measured in polycrystalline silicon doped with boron. After increasing the annealing temperature and the dopant dose, spectral broadening was observed in the high‐energy side of the Si peak. The fraction of boron at the substitutional position was estimated by the intensity ratio between the Si‐B local mode and the Si optical phonon mode. This ratio was proportional to the hole carrier densities, and, as a result, estimation of the hole carrier densities was also possible. Raman scattering is applicable for the estimation both of boron at the substitutional position and of hole carrier densities.