We designed a nickel-assisted process to obtain graphene with sheet resistance as low as 80 Ω square−1 from silicon carbide films on Si wafers with highly enhanced surface area. The silicon carbide film acts as both a template and source of graphitic carbon, while, simultaneously, the nickel induces porosity on the surface of the film by forming silicides during the annealing process which are subsequently removed. As stand-alone electrodes in supercapacitors, these transfer-free graphene-on-chip samples show a typical double-layer supercapacitive behaviour with gravimetric capacitance of up to 65 F g−1. This work is the first attempt to produce graphene with high surface area from silicon carbide thin films for energy storage at the wafer-level and may open numerous opportunities for on-chip integrated energy storage applications.