Chlorinated organic pollutants widely exist in aquatic environments and threaten human health. Catalytic approaches are proposed for their elimination, but sluggish degradation, incomplete dechlorination, and catalyst recovery remain extremely challenging. Here we show efficient dechlorination using ferrous oxide/graphene oxide catalytic membranes with strong nanoconfinement effects. Catalytic membranes are constructed by graphene oxide nanosheets with integrated ultrafine and monodisperse sub-5 nm nanoparticles through simple in-situ growth and filtration assembly. Density function theory simulation reveals that nanoconfinement effects remarkably reduce energy barriers of rate-limiting steps for iron (III)-sulfite complex dissociation to sulfite radicals and dichloroacetic acid degradation to monochloroacetic acid. Combining with nanoconfinement effects of enhancing reactants accessibility to catalysts and increasing catalyst-to-reactant ratios, the membrane achieves ultrafast and complete dechlorination of 180 µg L-1 dichloroacetic acid to chloride, with nearly 100% reduction efficiency within a record-breaking 3.9 ms, accompanied by six to seven orders of magnitude greater first-order rate constant of 51,000 min-1 than current catalysis. Meanwhile, the membranes exhibit quadrupled permeance of 48.6 L m-2 h-1 bar-1 as GO ones, because nanoparticles adjust membrane structure, chemical composition, and interlayer space. Moreover, the membranes show excellent stability over 20 cycles and universality for chlorinated organic pollutants at environmental concentrations.