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We have fabricated BiFeO3 thin film deposited on Pt/Ti/SiO2/Si substrates by the chemical solution deposition method. The effects of annealing temperature on the thin film structure, resistance switching (RS) properties, conduction mechanisms are investigated. It exhibits improved RS window with high ON/OFF ratio ([Formula: see text]104) for the sample annealed at 650[Formula: see text]C. XPS characterization indicates that cation ratio of Fe[Formula: see text]/Fe[Formula: see text] is increased with increasing annealing temperature. Crystal lattice distortion generated by Fe[Formula: see text] cations, along with oxygen vacancies, commonly contribute to opening the RS window and the increment of conductive filaments. The film’s conduction mechanisms under different annealing temperatures are fully discussed. The RS properties of this system can be effectively improved by increasing the annealing temperature, which is crucial prerequisite for future applications of BFO-based thin film device in resistance random access memory.