BACKGROUNDPrinting and dyeing reverse osmosis concentrates (ROC) contain large amounts of salts and organic matter, which is a major environmental issue. The unique composition of such wastewater makes the use of traditional physicochemical techniques challenging.RESULTSIn this paper, titanium dioxide nanotube arrays/SnO2‐Sb2O3 (Ti‐NTA/SnO2‐Sb2O3) electrodes were prepared by anodizing–cathodizing and sol–gel method for the electrocatalytic degradation of printing and dyeing ROC. Organic matter removal under different situations was examined, and the best treatment parameters were identified.CONCLUSIONFollowing treatment, organic matter concentration dropped from 1600 to 50 mg L−1, or even less. The outstanding removal performance of the Ti‐NTA/SnO2‐Sb2O3 electrode was validated by full‐scan ultraviolet spectra, gas chromatography–mass spectrometry and three‐dimensional fluorescence. Evaluation of the dissolved heavy metals and halogenated degradation process byproducts revealed that the electrocatalytic membranes were environmentally safe. These findings highlight the enormous potential of electrocatalytic membranes for the treatment of high‐salt ROC when equipped with a Ti‐NTA/SnO2‐Sb2O3 electrode. © 2024 Society of Chemical Industry (SCI).