Transition metal-based catalysts used in advanced oxidation processes may encounter problems of metal ion leaching. Therefore, advanced oxidation processes initiated by metal-free carbon catalysts are regarded as competitive solutions for environmental remediation. In light of this, we have prepared PAF-145, a porous aromatic framework containing carbonyl groups (C = O) that serves as a stable and eco-friendly metal-free carbon catalyst for activating peroxymonosulfate. The stable structure and abundant C = O groups of PAF-145 endow it with excellent degradation performance, good reusability and adaptability to a wide pH range and environments with various coexisting anions. PAF-145 degraded 98.7 % of Rhodamine B within 20 min, achieving a reaction rate constant that was 48.5 times higher than that of PAF without carbonyl groups. PMS is oxidized to 1O2 and O2•− on the electron-deficient carbon atoms within the carbonyl groups. Using quenching experiments, electron paramagnetic resonance analysis, and electrochemical tests, it was determined that the degradation of Rhodamine B is primarily governed by both a non-radical pathway that includes 1O2 and the electron transfer mechanism, as well as a radical pathway that involves O2•− in the PAF-145/PMS system.