Ceramic nanofiltration (NF) is a newly-developed technology for water recycling, but is still limited to pilot-scale applications. Lacking efficient and eco-friendly strategies for cleaning ceramic NF membrane impedes its scaling-up in industries. Forward flush, backwash and acidic/caustic cleaning are not efficient enough. In this work, a novel oxalic acid-aided Fenton process was proposed for synergistic relaxation/oxidation of persistent Ca2+-mediated gel-like fouling of ceramic NF membrane. A reactive catalyst layer was online pre-coated on top of the membrane via a pressure-driven cross-flow pre-filtration of Fe3O4 hydrosols. The gel-like fouling was simulated by alginate in the presence of Ca2+ ions. Results show that the Fe3O4 loading could be readily tuned from 0.16 to 1.34 g m−2 by altering the permeate flux during the pre-coating. The membrane permeability loss due to the pre-coating was minimal (<10%). The combination of oxalic acid chelation and Fenton-based oxidation resulted in high flux recovery (85.07%) for the iron-oxide pre-coated membrane, whereas the single treatment by hydrogen peroxide (H2O2) or oxalic acid was inefficient. This synergistic effect was attributed to relaxation of the Ca2+-mediated gel layer via oxalic acid/Ca2+ chelation, which presumably facilitated H2O2 diffusion at the Fe3O4/foulant interface. The iron-oxide pre-coated membrane maintained stable initial normalized fluxes (83.33–90.15%) through the oxalic acid/H2O2 cleaning over five cycles, with no need of refreshing the iron-oxide pre-coat. Additionally, the leaching of iron from the iron-oxide pre-coat by oxalic acid was suppressed by the oxalic acid/H2O2 combination, owing to a reactive shielding by competitive sorption of H2O2 onto the Fe3O4 surface. Overall, the synergistic relaxation/oxidation method, demonstrated in this study, provides new insights into improving reactivity of Fenton-based processes on hybrid catalytic ceramic membranes for water treatment or fouling control.@en