A Ca_0.5(Na_0.5Bi_0.5)_0.5-3x(Li_0.5Ce_0.5)_3xBi₂TaNb_0.99Mn_0.01O₉(CNBTNM-LC100x) solid-solution piezoelectric ceramic with high Curie temperature (T_C) was prepared using the traditional solid-state reaction method. The effect of Li, Ce composite iondoping on the ceramic structure and electrical properties was studied. The results show that, with increasing Li, Ce doping concentration, the crystal structure of CNBTNM-LC100x ceramics tends to transition from orthogonal to tetragonal, and the piezoelectric constant d₃₃ gradually increases. When the molar fraction x＞0.04, d₃₃ tends to decrease. When x=0.04, the ceramic sample exhibits the best comprehensive performance, with d₃₃≈15.9 pC/N, and the DC resistivity ρ≈5.9×10⁵ Ω·cmat 600 ℃.Further,the dielectric loss tan δ(1 MHz)≈7%,and T_C≈887 ℃.