Metal-free heterogeneous catalysts are receiving more and more attention for wastewater remediation by activating peroxymonosulfate (PMS) due to their environmental benign. However, carbon-based materials as the most typical metal-free heterogeneous always suffer from poor durability. Inspired by the fact that a conjugated system may facilitate the electron transfer during PMS activation, we innovatively select polyaniline (PANI) as a new PMS activator and investigate its catalytic performance in detail. It is found that PANI can display better catalytic performance than traditional metal-based catalysts and popular N-doped carbocatalysts in methyl orange (MO) degradation. More importantly, PANI is not only universal for various pollutants degradation but also maintains its catalytic performance in repeated degradation experiments. The stable N sites in the conjugated chains and the oxidation-resistance benzene rings as the building units are considered to be responsible for such an excellent durability. In addition, the influences of some routine factors and actual water backgrounds are comprehensively checked and analyzed. The quenching experiments and electron paramagnetic resonance confirm that MO degradation is achieved through both radical and nonradical pathways, where SO4•- and 1O2 are primary reactive species. The reaction mechanism is also proposed with the assistance of X-ray photoelectron spectroscopy.