Here, hierarchically porous carbons are synthesized by carbonation under N2 atomsphere with glucose as carbon precursor and NaNO3 as the template. Then the samples are treated with NH3 at high temperature to obtain nitrogen doped porous carbons, which are labeled as NC-X-T (X refers to the weight ratio of NaNO3 and glucose, and T/oC refers to the annealing temperature). These materials are then characterized by N2 adsorption-desorption, XRD, XPS, SEM, and TEM to show their surface areas, pore size distribution, crystal structure, chemical composition, and morphologies detailly. Taking phenol as the model pollutant and peroxymonosulfate (PMS) as the oxidant, the effects of different experimental conditions on their catalytic performance are studied. The experimental results show that the synergistic effect of pore engineering and nitrogen doping process can greatly improve the catalytic performance of the catalyst. With 0.01 g/L PMS and 0.005 g NC-0.5-800 added, 5.3×10-4 mol/L phenol in 100 mL can be completely degraded with a rate constant of 0.397 min-1, which is superior to most metal and non-metal catalysts. Moreover, the NC-0.5-800 after stability test is characterized by XPS, and the oxidation of carbon frame is found to be the direct reason for their deactivation, while the activity can be partly recovered by high temperature calcination under N2 atmosphere.