Bi1−xCexFeO3 (x=0, 0.05, 0.1, 0.15, and 0.20) (BCFO) thin films were deposited on Pt/TiN/Si3N4/Si and fluorine-doped SnO2 glass substrates by sol-gel technique, respectively. The effect of Ce doping on the microstructure, electrical and magnetic properties of BCFO films was studied. Compared to counterparts of BiFeO3 (BFO) film, the fitted Bi 4f7/2, Bi 4f5/2, Fe 2p3/2, Fe 2p1/2, and O 1s peaks for Bi0.8Ce0.2FeO3 film shift toward higher binding energy regions by amounts of 0.33, 0.29, 0.43, 0.58, and 0.49 eV, respectively. Raman redshifts of 2–4 cm−1 and shorter phonon lifetimes for the Bi0.8Ce0.2FeO3 film might be related to anharmonic interactions among Bi–O, Ce–O, (Bi, Ce)–O, and Fe–O bonds in the distorted oxygen octahedron. Compared to the pure counterparts, the dielectric and ferroelectric properties of the Bi0.8Ce0.2FeO3 film are improved due to the decreased oxygen vacancies by the stabilized oxygen octahedron. Current density values for the BFO and Bi0.8Ce0.2FeO3 film capacitors are 9.89×10−4 and...