•GONs doping boosted the electrooxidation ability of Ti4O7 REM.•1wt% GONs doping significantly reduced the charge-transfer resistance.•The •OH yield of 1%GONs@Ti4O7 REM improves 2.5–2.8 times.•GONs doping can facilitate the stability of Ti4O7 REM.•Energy cost (EE/O) for treating 1,4-D was observed at only 0.34–0.74 kWh/m3. Although Ti4O7 ceramic membrane has been recognized as one of the most promising anode materials for electrochemical advanced oxidation process (EAOP), it suffers from relatively low hydroxyl radical (•OH) production rate and high charge-transfer resistance that restricted its oxidation performance of organic pollutants. Herein, we reported an effective interface engineering strategy to develop a Ti4O7 reactive electrochemical membrane (REM) doped by graphene oxide nanoparticles (GONs), GONs@Ti4O7 REM, via strong GONs–O–Ti bonds. Results showed that 1% (wt%) GON doping on Ti4O7 REM significantly reduced the charge-transfer resistance from 73.87 to 8.42 Ω compared with the pristine Ti4O7 REM, and yielded •OH at 2.5–2.8 times higher rate. The 1,4-dioxane (1,4-D) oxidation rate in batch experiments by 1%GONs@Ti4O7 REM was 1.49×10−2 min−1, 2 times higher than that of the pristine Ti4O7 REM (7.51×10−3 min−1) and similar to that of BDD (1.79×10−2 min−1). The 1%GONs@Ti4O7 REM exhibited high stability after a polarization test of 90 h at 80 mA/cm2, and within 15 consecutive cycles, its oxidation performance was stable (95.1–99.2%) with about 1% of GONs lost on the REM. In addition, REM process can efficiently degrade refractory organic matters in the groundwater and landfill leachate, the total organic carbon was removed by 54.5% with a single-pass REM. A normalized electric energy consumption per log removal of 1,4-D (EE/O) was observed at only 0.2–0.6 kWh/m3. Our results suggested that chemical-bonded interface engineering strategy using GONs can facilitate the EAOP performance of Ti4O7 ceramic membrane with outstanding reactivity and stability. Display omitted