Ferroelectric capacitors hold great promise for non-volatile memory applications. However, the challenge lies in fabricating resistive switching devices with a high on/off ratio, excellent non-volatility, and a simple manufacturing process. Here, a novel approach is introduced by demonstrating the efficacy of the coupling effect between ferroelectric polarization and oxygen vacancy-based conductive filaments in Hf0.5Zr0.5O2 (HZO) films for the creation of non-volatile resistive switching memory devices, achieving an impressive on/off ratio of 6.8 × 103 at +1.8 V. An in-depth exploration of the resistive switching mechanism is provided and subsequently the outstanding durability and retention characteristics of these devices for resistive switching is validated. Furthermore, the device’s capacity to emulate non-volatile synaptic functionalities is assessed. Our results reveal that under pulsed conditions of 1 V/–2 V with 1 µs pulses spaced 50 ms apart, the device can robustly achieve potentiation/depression synaptic plasticity, while exhibiting energy consumption (0.16 fJ for potentiation, 0.12 fJ for depression) reduced by 1–2 orders of magnitude compared to biological synapses. This work holds significant value as a reference for the fabrication of energy-efficient, non-volatile memory and synaptic devices.