A novel cathode film with aeration function was prepared using a polyphenylene sulfide (PPS) ultra-fine fiber and conductive carbon black (CB). The flexible and non-metallic PPS cathode film was applied in the electro-Fenton (e-Fenton) system in order to degrade the contaminants in wastewater. The effects of the current density, contaminant species, initial pH, and aeration rate on the degradation rate of contaminants were systematically studied. The results show that the optimized conditions include a pH of 3 and a current density of 16 A m(-2). It was found that the generation of H2O2 could be greatly enhanced, and several contaminants (methyl orange (MO), methylene blue (MB), rhodamine-B (RhB), malachite green (MG), Orange II (OII) and heptanaphthenic acid (HNA) could be efficiently degraded when the PPS cathode film was used in the e-Fenton system. This robust function of the e-Fenton system results from the benefits of the large porosity, good adsorptivity, and more active sites of the fabricated PPS cathode film. Additionally, the aeration function of the PPS cathode film strongly increased the removal rate of the contaminants. The PPS cathode film can be of potential application in the e-Fenton system for cost-efficient degradation of organic contaminants.