Design of metal-free photocatalysts with customized chemical structure and nano-architecture is promising for photocatalytic hydrogen peroxide (H₂O₂) production. Herein, for the first time, mesoporous resorcinol-formaldehyde (MRF) nanobowls with optimized benzenoid-quinoid donor-acceptor (D-A) couples have been synthesized via an assembly-hydrothermal-etching process as high-performance photocatalysts for H₂O₂ production in a sacrificial agent-free system. At the hydrothermal temperature of ~ 250 °C, MRF-250 exhibits optimized structural features including a large surface area, suitable D-A couple ratio, enhanced light absorption, charge-hole separation and mass transfer. Thus, MRF-250 shows an unexpected H₂O₂ yield of 19.4 mM·g^-1·h^-1 in pure water, outperforming other RF samples prepared under different conditions and superior to most reported metal-free photocatalysts without the aid of sacrificial agents. Our work paves the way towards the elaborate design of highly effective metal-free photocatalysts for H₂O₂ production.