Artificial photosynthesis is a critical challenge in moving towards a sustainable energy future. Photocatalytic generation of hydrogen peroxide from water and dioxygen (H2O + 1/2O(2) -> H2O2, Delta G degrees = 117 kJ mol(-1)) by sunlight is a promising strategy for artificial photosynthesis because H2O2 is a storable and transportable fuel that can be used directly for electricity generation. All previously reported powder photocatalysts, however, have suffered from low efficiency in H2O2 generation. Here we report that resorcinol-formaldehyde resins, widely used inexpensive polymers, act as efficient semiconductor photocatalysts to provide a new basis for H2O2 generation. Simple high-temperature hydrothermal synthesis (similar to 523 K) produces low-bandgap resorcinol-formaldehyde resins comprising pi-conjugated and pi-stacked benzenoid-quinoid donor-acceptor resorcinol couples. The resins absorb broad-wavelength light up to 700 nm and catalyse water oxidation and O-2 reduction by the photogenerated charges. Simulated sunlight irradiation of the resins stably generates H2O2 with more than 0.5% solar-to-chemical conversion efficiency. Therefore, this metal-free system shows significant potential as a new artificial photosynthesis system.