In the current study, to promote peroxymonosulfate (PMS) activation efficiency of visible-light-driven (VLD) photocatalysis of g-C3N4 (CN) (VLD/CN/PMS) process, electrochemical (EC) process was introduced to assist VLD/CN/PMS process to construct a coupled process (EC + VLD/CN/PMS). Compared to single VLD/CN/PMS, EC assisting CN activating PMS (EC/CN/PMS), and CN activating PMS (CN/PMS) process, EC + VLD/CN/PMS process exhibited an apparently boosted PMS activation efficiency toward TC degradation due to the interaction effect of EC and VLD photocatalysis process promoting the PMS adsorption on CN surface. It shows that surface radicals and electron-transfer mechanism in the EC + VLD/CN/PMS process made the dominant contribution to TC degradation, which was evidenced by the quenching experimental results, EPR test, and electrochemical analysis. Noticeably, the EC + VLD/CN/PMS process exhibited strong resistance to the coexisting anions even with a high concentration (200 mM) in water, as the PMS adsorption capacity was little affected by those anions, with wide pH adaptability (3–11), high stability, and universal applicability for various organics. In addition, based on the detected intermediates and density functional theory (DFT) calculations, the pathways of TC degradation were revealed in detail. In brief, EC + VLD/CN/PMS process was proved to be a reliable technology for antibiotic pollutant removal.