Zn:Fe:LiNbO3 crystals with different Li/Nb ratios in the melts (Li/Nb = 0.946, 0.97, 1.00, 1.10, 1.20, 1.44) have been grown for the first time. The UV-Vis absorption spectra, exponential gain coefficient, diffraction efficiency and response time of the crystals were measured. With the ratio of Li/Nb increasing, the absorption edge shifts to a shorter wavelength, the exponential gain coefficient and response speed increase, but the diffraction efficiency decreases.