The effect of Zn2+ ion on the dopant occupancy and optical characteristic of Er3+ ion in Er/Zn-codoped LiNbO3 crystal is reported. The intense 1.54 渭m and relatively weak green upconversion emissions are observed for Er (1 mol%)/Zn (6 mol%):LiNbO3 crystal. The OH鈭?/sup> absorption and the time-resolved spectra show that the Zn2+ codoping decreases the threshold concentration of Er3+ ion in Er/Zn-codoped LiNbO3 crystal. The experimental results here imply that the potential application of Er3+-doped LiNbO3 crystal can be designed and optimized on the basis of the theoretical investigations.