Two-dimensional (2D) graphene has shown great potential of breakthrough of Moore’s law limitation due to its atomic thickness in electronic devices. Up to now, chemical vapor deposition (CVD) is a widely applied method for graphene growth due to its low-cost, large-area production, and easy control in layer number. However, the CVD-grown graphene usually suffers from relatively low quality derived from the polycrystalline nature of catalytic metal (e.g., Cu) substrates. Herein, single-crystal Cu (111) substrates were fabricated by a high-temperature annealing process, initial nucleation of graphene on it has been well controlled, and high-quality and centimeter-size single-crystal graphene was achieved. The Cu (111) substrate provides onefold orientation for the graphene growth according to their lattice matching relation, and domain boundaries of neighboring graphene nuclei could stitch together. The as-grown single-crystal graphene has an average sheet resistance of 607.5 Ω · sq-1. Compared to that of grown on the pristine polycrystalline Cu (1 415.7 Ω · sq-1), it shows high electrical conductivity. High-temperature annealing purified the Cu foils, and induced a clean graphene surface with lower roughness. The quality of graphene is further verified by using it in a field-effect transistor (FET), resulting in a maximum switch ratio of 145.5 and carrier mobility of 2.31×103 cm2 · V-1 · s-1. Based on these results, we believe that the single-crystal graphene in present work is also feasible for fabricating other high-performance electronic devices.