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[Display omitted] • Introduing N defects over g-C 3 N 4 significantly increased photocatalytic activity. • An IEF was built to further strengthened the transport of photoexcited carriers. • The excellent O 2 adsorption capacity promoted H 2 O 2 production via 2e− ORR. • A possible H 2 O 2 generation pathway formed via 1O 2 was proposed. The development of photocatalysts for the efficient generation of hydrogen peroxide (H 2 O 2) and degradation of antibiotic pollutants is a mutual-beneficial solution to the chemical resource demands and environmental remediation. Herein, efficient visible-light-driven H 2 O 2 production and antibiotic degradation are achieved by using nitrogen-deficient modified polymeric carbon nitride (g-C 3 N 4) to facilitate the reduction of dioxygen. The N defects modified g-C 3 N 4 reached an excellent H 2 O 2 generation rate of 623.5 μmol g−1h−1 without O 2 bubbling. The structural features and entire photocatalytic conversion process were systematically studied via experiments and theoretical calculations. It was found that the N defects in the framework constructed a giant internal electric field (IEF), which effectively inhibited carrier recombination. Revealed the neglected H 2 O 2 production via 1O 2 pathway, which effectively promoting the selective 2e− oxygen reduction reaction (ORR). More interestingly, the N defects structure greatly improved the O 2 adsorption ability and O 2 production ability of the material, while inhibiting the in situ generated H 2 O 2 from being decomposed and maintaining high efficiency of H 2 O 2 production under air conditions. This study thoroughly revealed the synergistic effects of the terminal cyano group and nitrogen vacancies over g-C 3 N 4 for efficient H 2 O 2 photogeneration photosynthesis. [ABSTRACT FROM AUTHOR]