In this paper, the bismuth-layered structure piezoelectric ceramics (Ca,Sr)Bi4Ti4O15 doped with CeO2 are prepared by the solid state reaction method. The crystal structure of the ceramics is determined by X-ray diffraction and the single orthorhombic structure phase is found. However, the doping of CeO2 increase the lattice parameters a, b, c. As a result, the ions of Ce enter into the lattice of the bismuth-layered structure and occupy A sites in the perovskite layer of bismuthlayered structure lattice. The temperature dependence of the conductivity shows that the resistivity increases by doping of CeO2 and reaches its maximum when the doping content is 0.4mol%. The mechanism of the CeO2 doping is also analyzed. By the investigation of XPS, the Ce ions have two types of valences: Ce3+ and Ce4+. The existence of Ce ions strengthened the weak Bi-O bonding and decreased the oxygen vacancies in the lattice, so the ceramics have lower conductivity.