In C3v point group symmetry, crystal field energy levels of Yb3+ in LiNbO3 were assigned on the basis of DSCPCF model and PCF model. As compared with the experimental values of crystal field energy levels, the root mean square standard deviation is 16.09cm-1 for the calculation of the DSCPCF model and is 30.30cm-1 for the PCF, respectively. This result shows that the DSCPCF model can fit the experimental values of crystal field energy levels better than the PCF model. At the same time, Absorption spectra and Emission spectra of Yb3+ in LiNbO3 were analyzed and the peaks that appear in Figures were also assigned reasonably.