Metal-free catalysis for green degradation of aqueous organic pollutants has caused extensive concern in recent years. In this study, hexagonally-ordered mesoporous carbon (CMK-3) was applied to activate persulfate (PS) for the degradation of 2,4-dichlorophenol (2,4-DCP) with superior removal rate of 90% in 20 min. The high catalytic efficiency was probably ascribed to the accelerated electron transfer resulting from the large adsorption capacity of CMK-3. It was found that specific surface areas (SSA), defective sites and functional groups on the activator were highly related to its catalytic efficiency and passivadon. Compared to other nanocarbons, CMK-3 had better reusability due to its ordered mesoporous structure with large SSA and high defective degrees. For the first time, a two-pathway mechanism was proposed for metal-free activation process of PS, indicating that radical and nonradical oxidation worked together in PS activation for complete 2,4-DCP decomposition, and non-radical pathway played a dominant role while radical pathway was critical in accelerating the reaction. center dot OH, SO(4)(center dot-)and O-2(center dot)- all took part in the radical oxidation process, in which the contribution of center dot OH was dominant. Besides, high decomposition efficiency was also achieved in pharmaceutical wastewater treatment by the CMK-3/PS system. This research proposed a new electron transfer mechanism for metal-free activation process of PS, which can provide a theoretical support for further studies.