Three-dimensional nanoporous nitrogen-doped graphene (3D-PNG) has been synthesized through a facial one-step synthesis method without additional silica template. The as-prepared 3D-PNGwas used as an electrocatalyst for the oxygen reduction reaction (ORR), which shows excellent electrochemistry performance, demonstrated by half-cell electrochemical evaluation in 0.1 M KOH including prominent ORR activity, four electron-selectivity and remarkable methanol poisoning stability compared to commercial 20%Pt/C catalyst. The physical and surface properties of 3D-PNG catalyst were characterized by scanning electron microscopy (SEM), high-resolution transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and BET surface area analysis. The experiments show that 3D-PNG catalyst possesses super-large specific surface area reaching 920 m²g⁻¹, which is superior to our most recently reported 3D-PNG synthesized by silica template (670 m²g⁻¹) and other doped graphene catalysts in literature. When used for constructing a zinc–air battery cathode, such an 3D-PNG catalyst can give a discharge peak power density of 275 mW cm⁻². All the results announce a unique procedure to product high-efficiency graphene-based non-noble metal catalyst materials for electrochemical energy devices including both fuel cells and metal–air batteries.