Nitrogen-doped graphene nanoribbon (N-GNR) nanomaterials with different nitrogen contents have been facilely prepared via high temperature pyrolysis of graphene nanoribbons (GNR)/polyaniline (PANI) composites. Here, the GNRs with excellent surface integration were prepared by longitudinally unzipping the multiwalled carbon nanotubes. With a high length-to-width ratio, the GNR sheets are prone to form a conductive network by connecting end-to-end to facilitate the transfer of electrons. Different amounts of PANI acting as a N source were deposited on the surface of GNRs via a layer-by-layer approach, resulting in the formation of N-GNR nanomaterials with different N contents after being pyrolyzed. Electrochemical characterizations reveal that the obtained N8.3-GNR nanomaterial has excellent catalytic activity toward an oxygen reduction reaction (ORR) in an alkaline electrolyte, including large kinetic-limiting current density and long-term stability as well as a desirable four-electron pathway for the formation of water. These superior properties make the N-GNR nanomaterials a promising kind of cathode catalyst for alkaline fuel cell applications.