The laser-micro-Raman spectra of near-stoichiometric LiNbO3 crystals were measured and analyzed. The crystals were grown by flux pulling method. Compared with the congruent LiNbO3 crystal, the number and frequency of Raman spectral lines of A1(TO) and E(TO) modes have no change. It was validated that the LiNbO3 crystal is substitutional solid solution. The relative intensity of 738cm-1 Raman peak(A1(LO)) exhibited obvious change when the Li2O contents increase in pure LiNbO3 crystal, the 738cm-1 Raman peak disappeared in the Mg-doped and Zn-doped LiNbO3 crystals. These Raman peaks were discussed and explained from the occupied site and structure according to the Li vacancy model. The full width at half maximum (FWHM) of the 152 and 872cm-1 Raman peaks narrows with increasing the Li/Nb in the crystals. Their relationships were fitted linearlly, using the fitting equation, and the Li/Nb ratio can be calculated according to the FWHM of Raman peaks.