The growth of LiNbO3 crystals co-doped with Zn2+, Eu3+ ions with different concentrations by Bridgman method was obtained by means of the feed materials with proper composition mole fraction [x(Li2O)=48.6%, x(Nb2O5)=51.4%]. The X-ray diffraction (XRD), excitation, emission and phonon side band spectra of the upper and lower parts of crystals were measured. The doping content of ZnO takes great effects on the distributing concentration of Eu3+ ion LiNbO3 crystal. When 3% of ZnO in mole fraction is doped, the Eu3+ ions are suppressed effectively to enter LiNbO3 crystal lattice, but in 6% mole fraction, the effect becomes weaker. The reasons for the concentration changes of Eu3+ ions can be interpreted by the suppressing effect of ZnO on the incorporation of Eu3+ ions and the change of distribution coefficient of Zn2+ as its incorporating content. In the meantime, the phonon sideband spectra of Zn-incorporated samples were recorded.