A high-surface-area conductive cellular carbon monolith is highly desired as the optimal electrode for achieving high energy, power, and lifetime in electrochemical energy storage. 3D graphene can be regarded as a first-ranking member of cellular carbons with the pore-wall thickness down to mono/few-atomic layers. Current 3D graphenes, derived from either gelation or pyrolysis routes, still suffer from low surface area, conductivity, stability, and/or yield, being subjected to methodological inadequacies including patchy assembly, wet processing, and weak controllability. Herein, a strategy of zinc-assisted solid-state pyrolysis to produce a superior 3D graphene is established. Zinc unprecedentedly impregnates and delaminates a solid (“nonhollow”) char into multiple membranes, which eliminates the morphological impurities ever-present in the previous pyrolyses using solid-state carbon precursors. Zinc also catalyzes the carbonization and graphitization, and its in situ thermal extraction and recycling enables the scaled-up production. The created 3D graphene network consists integrally of morphologically and chemically pure graphene membranes. It possesses unrivaled surface area, outstanding stability, and conductivity both in air and electrolyte, exceeding preexisting 3D graphenes. The advanced 3D graphene thus equips a porous monolithic electrode with unparalleled energy density, power density, and lifetime in electric-double-layer capacitive devices.