The electrocoagulation/ultrafiltration (ECUF) process is expected to address the issues of current wastewater increments and complex water reuse. However, the underlying mechanism associated with flocs remains unclear in the ECUF system, especially in the upgraded permanganate-bearing ECUF (PECUF) system. Herein, flocs and their formation, response to organic matter (OM), and interfacial features in the PECUF process were systematically explored. Results demonstrated that permanganate contributed to the rapid start-up of the coagulation process by forming MnO 2 and blocking the ligand−metal charge transfer process between adsorbed Fe(II) and solid-phase Fe(III). The response of flocs to natural OM (NOM) exhibited obvious time-and particle size-dependent characteristics. Based on this, the optimal NOM adsorption window was found to be in the interval of 5−20 min, whereas the optimal NOM removal window was located at the 20−30 min interval. Furthermore, the extended Derjaguin−Landau− Verwey−Overbeek theory revealed the underlying principle of the PECUF module for optimizing UF performance. On the one hand, it reduced the inherent resistance of the cake layer by modifying the colloidal solution, which guaranteed a small drop (15%) in initial flux. On the other hand, it enhanced the repulsive force among suspended particles to achieve a long-term antifouling effect. This study may provide insights into the selection and performance control of on-demand assembly modules in decentralized water treatment systems.