Nitrogen-doped graphene (NG) was synthesized through the chemical vapor deposition (CVD) of graphene on Cu substrates, which were pre-implanted with N ions by the ion implantation method. The pre-implanted N ions in the Cu substrate could dope graphene by the substitution of C atoms during the CVD growth of graphene, forming NG. Based on this, NG’s long-term protection properties for Cu were evaluated by ambient exposure for a corrosion test. The results showed that NG can obviously reduce the natural oxidation of Cu in the long-term exposure compared with the case of pristine graphene (PG) coated on Cu. Moreover, with the increase in pre-implanted N dose, the formed NG’s long-term protection for Cu improved. This indicates that the modification of graphene by N doping is an effective way to improve the corrosion resistance of the PG coating owing to the reduction in its conductivity, which would inhibit galvanic corrosion by cutting off electron transport across the interface in their long-term protection. These findings provide insight into corrosion mechanisms of the graphene coating and correlate with its conductive nature based on heteroatoms doping, which is a potential route for improving the corrosion resistance of graphene as an effective barrier coating for metals.