In this study, chitosan, a low-price and easily obtainable natural polymerized sugar containing abundant nitrogen element, was employed as a precursor for preparing hierarchically porous carbon (PC) to activate peroxymonosulfate (PMS). The PC fabricated at 800 °C obtained the optimum catalytic performance with complete removal of p-hydroxybenzoic acid (HBA) in 30 min. The selective degradation toward phenolic pollutants with different substituent groups and the resistance over the interference of typical anions and natural organic matter implied a non-radical pathway contributed most for HBA degradation. The investigation of structure-activity relationship suggested a positive linear correlation between graphitic N content and HBA removal. The chemical quenching experiment and electron paramagnetic resonance (EPR) excluded the crucial role of radicals and 1O2. Solid evidence based on electrochemical techniques demonstrated the essential contribution of electron transfer pathway achieved by three successive processes including the first close adsorption of PMS by PC800 to form metastable intermediates, then an internal electron transfer from active graphitic N to PMS within metastable intermediates and finally external electron transfer from HBA to metastable intermediates. This study provided insightful mechanism understanding of a promising organics elimination strategy by PMS activation through N-doped carbonaceous materials utilizing chitosan as a simultaneous carbon and nitrogen precursor.