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Photocatalysis provides a sustainable pathway to produce the consumer chemical H2O2from atmospheric O2via an oxygen reduction reaction (ORR). Such an alternative is attractive to replace the cumbersome traditional anthraquinone method for H2O2synthesis on a large scale. Carbon nitrides have shown very interesting results as heterogeneous photocatalysts in ORR because their covalent two-dimensional (2D) structure is believed to increase selectivity toward the two-electron process. However, an efficient and scalable application of carbon nitrides for this reaction is far from being achieved. Poly(heptazine imides) (PHIs) are a more powerful subgroup of carbon nitrides whose structure provides high crystallinity and a scaffold to host transition-metal single atoms. Herein, we show that PHIs functionalized with sodium and the recently reported fully protonated PHI exhibit high activity in two-electron ORR under visible light. The latter converted O2to up to 1556 mmol L–1h–1g–1H2O2under 410 nm irradiation using inexpensive but otherwise chemically demanding glycerin as a sacrificial electron donor. We also prove that functionalization with transition metals is not beneficial for H2O2synthesis, as the metal also catalyzes its decomposition. Transient photoluminescence spectroscopy suggests that H-PHIs exhibit higher activity due to their longer excited-state lifetime. Overall, this work highlights the high photocatalytic activity of the rarely examined fully protonated PHI and represents a step forward in the application of inexpensive covalent materials for photocatalytic H2O2synthesis.