Graphene is a single sheet of carbon atoms with outstanding electrical and physical properties and is being exploited for applications in electronics, sensors, photovoltaics, and energy storage. A novel 3D architecture called a pillared graphene nanostructure (PGN) is a combination of two allotropes of carbon, including graphene and carbon nanotubes. A one-step chemical vapor deposition process for large-area PGN fabrication via a combination of surface catalysis and in situ vapor–liquid–solid mechanisms is described. A process by which PGN layers can be transferred onto arbitrary substrates while keeping the 3D architecture intact is also described. Single and multilayer stacked PGNs are envisioned for future ultralarge and tunable surface-area applications in hydrogen storage and supercapacitors.