A Fe2O3 film homojunction was orderly prepared by magnetron sputtering and a hydrothermal method. The Fe2O3 homojunction-based memristor exhibits an obvious self-selective effect as well as a typical analogue resistive switching (RS) memory behavior. A desirable self-rectifying voltage range (−1 to 1 V), stable resistance ratio, good cycling endurance (>104 cycles), and long retention time (>104 s) can be obtained from the Fe2O3 homojunction-based memristor. Oxygen vacancies (Vo) are inevitably generated during the growth of the Fe2O3 film. The self-selective analogue RS memory behavior is ascribed to the electron tunneling behavior between the potential barrier generated by the FeOx contact and the electron filling dynamic in the Vo-based traps. This work provides a simple method to prepare a self-selective analogue memristor and lays the foundation for the core device of neuromorphic computing.