Abstract Mesoporous carbon nitrides (MCN) with C 3 N 4 stoichiometry could find applications in fields ranging from catalysis, sensing, and adsorption–separation to biotechnology. The extension of the synthesis of MCN with different nitrogen contents and chemical structures promises access to a wider range of applications. Herein we prepare mesoporous C 3 N 5 with a combined triazole and triazine framework via a simple self‐assembly of 5‐amino‐1 H ‐tetrazole (5‐ATTZ). We are able to hybridize these nanostructures with graphene by using graphene–mesoporous‐silica hybrids as a template to tune the electronic properties. DFT calculations and spectroscopic analyses clearly demonstrate that the C 3 N 5 consists of 1 triazole and 2 triazine moieties. The triazole‐based mesoporous C 3 N 5 and its graphene hybrids are found to be highly active for oxygen reduction reaction (ORR) with a higher diffusion‐limiting current density and a decreased overpotential than those of bulk g‐C 3 N 4 .