摘要： Photocatalytic H2 production based on g-C3N4 faces enormous challenging issues including limited visible-light absorption, poor separation and transfer abilities of photo-generated electron-hole pairs. Herein, we realize the synergistic effect of nanostructure engineering and electronic modulation with a supramolecular assembly mediated synthesis of heteroatom doped g-C3N4 hierarchical mesoporous spheres. The favorable doping site and possible effect on electronic structure are disclosed by DFT calculation with supporting experimental analysis. Impressively, S-doped g-C3N4 delivers a 13.2 times higher H2 production rate than bulk g-C3N4 under visible-light. More importantly, as the dual functional photocatalyst for H2 production and selective oxidation of benzyl alcohol, it can exhibit outstanding activity with a H2/benzaldehyde production rate of 3.76/3.87 μmol h-1, respectively. This work not only provide a new rationale for photocatalytic performance enhancement, but also shed new light on the highly efficient utilization of solar energy by coupling H2 generation with value added chemical production.