A series of Er3+ doped and Er3+/Yb3+ co-doped 0.96Na0.5Bi0.5TiO3-0.04CaTiO3(NBT-CT∶xEr3+/yYb3+,x=0.002~0.015, y=0.010) lead-free piezoelectric ceramics were prepared by a solid-state sintering method. The phase structure and up-conversion luminescence properties of the samples were characterized and analyzed by X-ray diffraction and fluorescence spectrofluorometer, respectively. These results show that the main crystal phase of the samples is that of NBT. Under the excitation of a 980 nm near-infrared light, the Er3+ doped and Er3+/Yb3+ co-doped NBT-CT ceramics exhibit characteristic emission of Er3+ with strong dominant green up-conversion emissions. The optimal up-conversion luminescence performance with x=0.010 in NBT-CT∶xEr3+ ceramics are obtained. Yb3+ can act as sensitizer and significantly enhance the up-conversion luminescence intensity of Er3+.