AbstractMemristors are recognized as crucial devices for the hardware implementation of neuromorphic computing. The conductance training process of memristors has a direct impact on the performance of neuromorphic computing. However, memristor breakdown and conductance decay still hinder the precise training process of neural networks based on passive memristor. Here, AlOx/LiNbO3 (LN) memristors are designed by inserting a AlOx sub‐oxide layer between the single‐crystalline LN thin film with oxygen vacancies (OVs) and Pt layer. Under the same training conditions, lower conductance and self‐compliance current effects are observed in AlOx/LN memristor. Slight spontaneous decay of conductance is achieved after the removal of the external stimulation. To explore the effects of AlOx sub‐oxide layer on the prevention of device breakdown and suppression of conductance decay, the memristive mechanism of devices with and without AlOx layer is revealed via time‐of‐flight secondary ion mass spectrometer (ToF‐SIMS). It is reasonable to believe that the AlOx inserting layer in memristors can serve as a self‐compliance current layer to inhibit device breakdown and provide the OVs reservoir to suppress conductance decay. These results offer new possibilities and theoretical grounds for achieving more reliable and precise conductance training of passive memristors.