Herein, we report a novel reactive nanostructured membrane (RNM) which integrated functionalities of effective peroxymonosulfate activation and advection-enhanced mass transfer rates, synthesized by anchoring nano-Co3O4 inside the nanochannel of Ti3C2 MXene as a co-catalyst, which was simultaneously embedded into a nickel foam support (denoted as Co/Ti3C2 RNM). The outstanding properties were mainly attributed to electron migration regulation through the nanoconfinement effect and the d-band center of the Co/Ti3C2 heterostructure close to the energy of the Fermi level. A 75.5 − 85.8% 1,4-dioxane (1,4-D) degradation in actual groundwater and bio-treated landfill leachate was achieved under a low pressure using a peristaltic pump and a high permeate flux of 237.8 L·m−2·h−1, corresponding to an ultrafast residence time of 3.7 s, in a single-pass flow-through mode. Singlet oxygen and Co(IV)-oxo species were mainly responsible for the 1,4-D removal. This study provides a strategy for the synthesis method of RNM combining the advantages of high catalytic activity and permeate flux.