Highly efficient electrochemical advanced oxidation processes (EAOPs) based on carbon catalysts are promising and green technologies for environmental remediation. Herein, for the purpose of cost-effectiveness, wide pH suitability and excellent reusability, graphite felt modified with regulatable N-doped graphene was developed as a cathode to electrochemically generate H2O2 with high yield and selectivity, and efficiently catalyze H2O2 to form (OH)-O-center dot for organic pollutants degradation by in-situ metal-free EAOPs. Particularly, the catalytic mechanism of N-doped graphene for enhanced performance was explored. Optimized N-doped graphene showed a very high H2O2 generation rate of 8.6 mg/h/cm(2), low electric energy consumption (9.8 kW h/kg) and high H2O2 selectivity of 78.02% in neutral pH solution. Compared with electro-Fenton (EF), this in-situ metal-free EAOPs on N-doped graphene displayed significant improvement on the degradation performance of organic pollutants in neutral and alkaline solutions, and was certified to be less affected by initial pH. The pyridinic N and C=C in N-doped graphene enhanced the onset potential while graphite N determined the disk current of oxygen reduction reaction (ORR) process. Most importantly, it proved that the introduction of graphite N could promote the 2e- ORR process for H2O2 generation, and the presence of pyridinic N could catalyze H2O2 to the production of (OH)-O-center dot. Taken phenol as target pollutant, 'OH generated by N-doped graphene accounted for 80.72% while O-2 contributed 19.28% to its degradation, based on which a possible mechanism for phenol degradation was proposed. Moreover, in-situ metal-free EAOPs showed excellent stability, reusability and performance for various organic pollutants degradation. This work would shed light on the catalytic mechanism for metal-free EAOPs, and thus promote its application for organic pollutants degradation.