The two inequivalent valleys in graphene are protected against long range scattering potentials due to their large separation in momentum space. In tailored √ 3N × √ 3N or 3N × 3N graphene superlattices, these two valleys are folded into Γ and coupled by Bragg scattering from periodic adsorption. We find that, for top-site adsorption, strong inter-valley coupling closes the bulk gap from inversion symmetry breaking and leads to a single-valley metallic phase with quadratic band crossover. The degeneracy at the crossing point is protected by C3v symmetry. In addition, the emergence of pseudo-Zeeman field and valley-orbit coupling are also proposed, which provide the possibility of tuning valley-polarization coherently in analogy to real spin for spintronics. Such valley manipulation mechanisms can also find applications in honeycomb photonic crystals. We also study the strong geometry-dependent influence of hollow-and bridge-site adatoms in the inter-valley coupling.