Visible light-driven H₂O₂ production presents the unique merits of sustainability and environmental friendliness. The size of noble metal nanoparticles (NPs) determines their dispersion and electronic structure and greatly affects their photocatalytic activity. In this work, a series of sized Au NPs over C₃N₄ were modulated for H₂O₂ production. The results show that there is a volcanic trend in H₂O₂ with the decrease of Au particle size, and the highest H₂O₂ production rate of 1052 μmol g⁻¹ h⁻¹ is obtained from medium-sized Au particles (∼8.7 nm). The relationship between structure and catalytic performance is supported by experimental and theoretical methods. (1) First, medium-sized Au NPs promote photon absorption, and have a suitable built-in electric field at the heterojunction, which can be successfully tuned to achieve a more efficient h⁺–e⁻ spatial separation. (2) Second, medium-sized Au NPs enhance O₂ adsorption, and create selective 2e⁻ O₂ reduction reaction sites. (3) Particularly, medium-sized Au NPs promote the desorption of produced H₂O₂ and inhibit H₂O₂ decomposition, finally leading to the highest H₂O₂ selectivity. Excellent catalytic performance will be obtained by finely optimizing the particle size in a certain range. This work provides a new idea for preparing high efficiently photocatalysts for H₂O₂ production.