Luminol-nitrogen doped graphene quantum dot (luminol-NGQDs) nanocomposite was synthesized and a novel electrochemiluminescence resonance energy transfer (ECL-RET) process occurred between luminol as the donor and NGQDs as the acceptor in the composite. This ECL-RET effect helped luminol-NGQDs composite produced an anodic ECL signal without coreactants. The ECL-RET mechanism was also studied based on the fluorescence spectra, the ultraviolet–visible absorption spectra and the electrochemiluminescence (ECL) spectra. Based on the significant sensitization effect of hydrogen peroxide on luminol-NGQDs ECL signal, an ECL method for the sensitive determination of hydrogen peroxide was established and then applied to the detection of hydrogen peroxide in water samples.