We　report　the　utilization　of　guanosine　as　a　supramolecular　precursor　that　unprecedentedly　renders　the　formation　of　carbon-based　multilayer　materials　with　naturally　high-level　nitrogen　doping.　As　a　proof-of-concept,　the　porous　carbon　multilayers　after　anchoring　0.5　wt%　Rh　electrocatalysts　displayed　an　excellent　hydrogen　evolution　reaction　activity.