The vacancies and nitrogen dopants significantly alter the interfacial bonding and electrical properties at the graphene/metal interface. The graphene/copper system, characterized by coherent and immiscible interfaces, serves as a suitable benchmark to elucidate the intrinsic interactions between carbon and metal atoms. Herein, the individual effects of vacancies and nitrogen dopants, as well as their combined effects, are systematically investigated. The bonding energies show that the interfacial bonding is the strongest at the monovacancy (MV) graphene/copper interface, indicating that the introduction of nitrogen in defective graphene/copper interfaces weakens the interfacial bonding. Furthermore, the band structures indicate that both vacancies and nitrogen dopants contribute to the formation of a bandgap. Among them, both MV and graphitic nitrogen doping significantly enhance interfacial bonding while maintaining relatively intact interfacial and band structures.