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A perovskite LaCoO 3 functionalized Ti 4 O 7 reactive electrochemical membrane (REM) was developed for electro-enhanced peroxymonosulfate (PMS) activation (E-REM-PMS), addressing limitations in wastewater treatment efficiency, reusability, and interference resistance. It achieved 100% carbamazepine (CBZ) removal at a rate constant of 39.69 min−1, 233 and 23 times of electro-REM (E-REM) system without PMS and REM-PMS system without electricity. In-situ Fourier transform infrared spectroscopy (FTIR) highlighted the promotion of electro-activation on PMS, while density functional theory (DFT) calculations elucidated mechanism differences under three adsorption configurations. 1O 2 (2.97×10−9 M), SO 4 • − (2.09×10−11 M) and •OH (7.36×10−12 M) dominated the E-REM-PMS system, consistent with sequence of reactive species by DFT results. Continuous treatment of pharmaceutical wastewater confirmed 100% CBZ removal and 60%-70% TOC mineralization at ultrahigh water flux (642.86 L/m2·h) with minimal energy consumption (0.01 kWh/m3·order). This work proposed a high-performance and anti-fouling REM, offering an efficient and economical solution for wastewater treatment. [Display omitted] • LaCoO 3 /T 4 O 7 REM achieved ultrafast CBZ removal in 10.6 s (100 %, k = 39.69 min−1). • ROS quantification and DFT calculation revealed the main role of 1O 2 , SO 4 • − and •OH. • In-situ FTIR proved synergistic effect of LaCoO 3 /T 4 O 7 REM, electric field and PMS. • This work showed high water flux (636.62 L/m2·h) with minimal energy consumption. • Long-term test in pharmaceutical wastewater clarified its practical applicability. [ABSTRACT FROM AUTHOR]