Bilayer graphene (BLG) can provide a tunable band gap when exposed to a vertical electric field. We report here an approach to the synthesis of large single-crystal BLG structures with diameters up to 0.54 mm. We found that both absorption-diffusion and gas-phase penetration mechanisms contributed to the growth of the lower second layer and that the absorption-diffusion mechanism favors faster BLG growth. Our strategy was to suppress nucleation in the growth of the first layer using an established surface oxidation method to maintain a low coverage of graphene on Cu foil. We subsequently maximized the growth of the second layer by increasing the duration of absorption-diffusion. The chemical treatment used to polish the Cu surface to reduce the nucleation of growth in the monolayer increased the nucleation density during the growth of the second layer. Electron transport measurements on dual-gated field-effect transistors showed that the BLG fabricated was of high quality with a sizeable tunable band gap. Our approach may have broad applications for the controlled synthesis of bilayers in materials chemistry.