A graphene-organic small molecule hybrid electrocatalyst (NG-TD) was prepared by a simple wet-chemical reaction between graphene oxide and the ortho-diamine-containing organic small molecule TPA-DAB. Due to the efficient doping of nitrogen atoms into the carbon-based network and the good structural restoration of the graphitic structures, NG-TD exhibits promising electrocatalytic activity for the oxygen reduction reaction (ORR) in alkaline electrolyte. Furthermore, the NG-TD hybrid electrocatalyst demonstrated additional advantages during the ORR process, such as high selectivity, excellent long-term stability, and very high resistance to methanol crossover.