4p/2p dual-doped monolayer and bilayer graphene were studied via first principle calculations. Generally, dopants prefer to be agglomerated. A second dopant significantly reduces formation energies. Thus, partially reduced graphene oxide would favor substitutional doping by facilitating the introduction of the 4p dopants. Dual-doping can tune the band gap from 0.1 to 0.8eV. For bilayer graphene, large atomic radii elements (Gallium and Germanium) form interlayer bonds with the undoped sheet. For some dual-doped graphenes, interlayer GaC and GeC bonds were formed, increasing the chemical reactivity of the undoped layer and affecting its electronic structure, with metallic or semiconducting characters observed.