A resistive switching device based on the stacked α-Fe2O3/Nb–SrTiO3 is proposed and fabricated that demonstrates excellent bipolar resistive switching behaviors including the uniformity, endurance, and retention performance. The Schottky-like current-voltage characteristics correlated with set process were observed in both high resistive states (HRSs) and low resistive states (LRSs) of the device. Importantly, the anticrosstalk characteristic, possessing higher reversed-biased LRS resistance than the forwarded-biased HRS resistance, indicates the potential applications of the stacked α-Fe2O3/Nb–SrTiO3 for multilevel storage in the cross-bar memory arrays. The carrier injection and trapping mechanism is suggested to explain the observed phenomena.