Polyphenylene sulfide (PPS) fiber products have been widely used for separation and filtration in harsh environments due to their excellent chemical resistance and relatively economical price. However, the poor temperature and weak oxidation resistance of PPS significantly shorten its service life under high temperature and strong oxidation environments. Herein, we report a type of oxidation-modified PPS (OPPS) fibers with excellent high temperature and oxidation resistance. This is achieved by oxidizing the thioether sulfide groups in PPS molecular chains into sulfoxide and sulfone groups and cross-linking the intermolecular chains. Both experiments and density functional theory (DFT) calculations indicate that hypochlorous acid (HClO) molecules can rapidly oxidize the PPS fiber surface. In addition, molecular dynamics (MD) simulations prove that there are strong hydrogen bonds and van der Waals interactions between HClO molecules and OPPS molecular chains, which promote the penetration of HClO molecules into the interior of the fiber to complete the layer-by-layer oxidation. The prepared OPPS-20 fibers exhibit excellent structural stability under high temperature and strong oxidant environments. Impressively, the OPPS-20 nonwoven filter still exhibits a high dust filtration efficiency of 99.95% after aging at 320 °C for 12 h, and the corresponding pressure drop is 24 Pa. In addition, the OPPS-20 nonwoven filter also maintains excellent filtration performance after aging in 60% HNO3 solution for 12 h, and the filtration efficiency and pressure drop are 99.96% and 29 Pa, respectively. This work demonstrates that the novel OPPS fibers have excellent application prospects in the field of separation and filtration in harsh environments.