Polycrystalline BiFeO3 thin films have been grown on glass substrates using a simple but efficient method commonly known as the spin coating technique. When used in a Cu / BiFeO3 / Cu configuration, the annealed BiFeO3 film (at 350 °C) exhibits bipolar resistive switching behaviour. The device shows stable resistive switching behaviour, where a stable hysteresis in the current–voltage curve was well developed by applying +/- 10 V at room temperature. The ratio of resistance in the high resistance state to the low resistance state of the device is ~ 104 with a good retention time of more than 106 min. The Poole–Frenkel emission at the Cu / BiFeO3 interface is proposed, and a redistribution of oxygen vacancies along the grain boundaries is found to play a key role in the resistance switching in the polycrystalline pure BiFeO3 films.