Bi2Sb3Cex and Bi2Sb3Ndx alloy films were prepared by PRC method (Pulse Reverse Current) in carbamide-NaBr-KBr-methanamide system. Their chemical composition was determined by EDS and the crystalline structure was analyzed by XRD. Under the optimal processing condition, there is a maximum filling quantity of the REE and the alloy films are composed of Bi2Sb3Ce2 and Bi2Sb3Nd0.1, which are rhombic hexahedral BiSb and tetrahedral cubic monoplasmatic Ce and Nd. The conductivity of Bi-Sb semiconductor pyroelectric materials stuffed by different REEs was also discussed