To realize graphene-based electronics, various types of graphene are required; thus, modulation of its electrical properties is of great importance. Theoretic studies show that intentional doping is a promising route for this goal, and the doped graphene might promise fascinating properties and widespread applications. However, there is no experimental example and electrical testing of the substitutionally doped graphene up to date. Here, we synthesize the N-doped graphene by a chemical vapor deposition (CVD) method. We find that most of them are few-layer graphene, although single-layer graphene can be occasionally detected. As doping accompanies with the recombination of carbon atoms into graphene in the CVD process, N atoms can be substitutionally doped into the graphene lattice, which is hard to realize by other synthetic methods. Electrical measurements show that the N-doped graphene exhibits an n-type behavior, indicating substitutional doping can effectively modulate the electrical properties of graphene. Our finding provides a new experimental instance of graphene and would promote the research and applications of graphene.