A simple one-step method is presented for synthesizing large single crystal graphene domains on melted copper using atmospheric pressure chemical vapour deposition (CVD). This is achieved by performing the reaction above the melting point of copper (1090 °C) and using a molybdenum support to prevent balling of the copper from dewetting. By controlling the amount of hydrogen during growth, individual single crystal domains of monolayer graphene greater than 200 µm are produced, determined by electron diffraction mapping. Angular resolved photoemission spectroscopy is used to show the graphene grown on copper exhibits a linear dispersion relationship and has no sign of doping.