Using both first-principles techniques and a real-space Kubo-Greenwood approach, electronic and transport properties of nitrogen-doped graphene with a single sublattice preference are investigated. Such a breaking of the sublattice symmetry leads to the appearance of a true band gap in graphene electronic spectrum even for a random distribution of the N dopants. More surprisingly, a natural spatial separation of both types of charge carriers at the band edge is predicted, leading to a highly asymmetric electronic transport. Both the presence of a band gap, allowing large on/off ratio, and an asymmetric transport pave a new route toward efficient graphene-based field-effect transistors.