The cerium modified 0.9Bi4Ti3O12–0.1K0.5Na0.5NbO3 (BTO-KNN) piezoelectric ceramics were synthesized using conventional solid state processing. The effects of cerium addition on the microstructure and electrical properties of BTO-KNN ceramics had been investigated in details. It was found that the ceramics possess a pure phase of bismuth oxide layer-type structure. The piezoelectric properties of BTO-KNN–based ceramics were significantly enhanced after cerium doping. The piezoelectric constant d33, dielectric loss tan δ, mechanical quality factor Qm and remanent polarization Pr for the BTO-KNN ceramics with 0.75 wt% CeO2 modification were found to be 28 pC/N, 0.29%, 2897, 11.83 μC/cm2, respectively, together with the high Tc ( ~ 615 °C) and stable piezoelectric properties, demonstrating that the cerium modified BTO-KNN piezoelectric ceramics are the promising candidates for high–temperature applications.