Hybridization of organometallic complexes with graphene-based materials can give rise to enhanced catalytic performance.U nderstanding the chemical structures within hybrid materials is of primary importance.I nt his work, archetypical hybrid materials are synthesized by the reaction of an organometallic complex, [Co II (acac) 2 ]( acac = acetylacetonate), with N-doped graphene-based materials at room temperature.E xperimental characterization of the hybrid materials and theoretical calculations reveal that the organometallic cobalt-containing species is coordinated to heterocyclic groups in N-doped graphene as well as to its parental acac ligands.The hybrid material shows high electrocatalytic activity for the oxygen reduction reaction (ORR) in alkaline media, and superior durability and methanol tolerance to aP t/C catalyst. Based on the chemical structures and ORR experiments,t he catalytically active species is identified as aCo-O 4 -N structure.Transition-metal-based organometallic compounds are an important class of molecular catalysts in various applications owing to their highly tunable properties,such as coordination numbers,o xidation states of metal centers,a nd binding structures between metals and ligands. [1] Their catalytic performances can be tuned by modulating electronic,c hemical, and steric interactions between the metal atoms and surrounding organic ligands.R ecently,i tw as reported that coordination of carbon-based nanomaterials,s uch as chemically modified graphenes (CMGs), carbon nanotubes,a nd carbon nitride,toorganometallic molecules can dramatically change catalytic performances. [2][3][4][5] Since carbon-based nano-