Raman measurements were carried out on Ho3+ doped Lithium Niobate crystals. When the excitation wavelength of 532nm is used, in addition of expected Raman modes, forbidden bands are detected, while when exciting with 785nm, “classical” Raman spectrum was recorded with expected modes according to Raman selection rules. Additional lines are attributed to emission lines of Ho doped crystals. We detect, within a very good resolution, in the same Stokes spectrum, the transitions between the electronic states, and the vibrational states as well. We report on the analysis of these data as function of Ho-content, for different polarizations and wavelengths, of the incident laser beam.