Using OTS as the template, Bi(NO₃)₃ and Fe(NO₃)₃ as the raw material and citric acid as the complexing agent, BiFeO₃ crystalline film was prepared on the glass substrate by the selfassembled monolayer technique. Effects of calcination and deposition temperatures on the BiFeO₃ film were explored. The physical phase composition, the microstructure and surface morphology of BiFeO₃ film were characterized by the testing methods, such as XRD, SEM and AFM. The energy detecting spectrum (EDS) provided the supporting evidence for the chemical composition of BiFeO₃ film. The results show that the pure BiFeO₃ crystalline film is prepared by the self-assembled monolayer technique after calcined at 600℃. In the deposition temperature range from 70℃ to 80℃, the BiFeO₃ film has better crystallinity with the homogeneous and dense surface.