The reaction of 2-pyridylamino-N,N-bis(2-methylene-4,6-dichlorophenol) (H2L) with CoCl2 affords a binuclear cobalt complex, [L-Co-µ2(OH)2-Co-L], which has been determined by using single crystal X-ray diffraction. Electrochemical studies show that this cobalt complex can serve as a molecular catalyst for oxygen reduction reaction (ORR). Under − 0.4 V vs Ag/AgCl, the H2O2 yield is 83% with 0.20 M KOH. Moreover, investigations exbibit that in homogeneous environments dissociation of a OH− ion from the binuclear cobalt complex makes positions on cobalt centres, letting dioxygen (O2) inserted and reduced. We hope these findings can provide a new ideal for the developments of electrocatalysts for ORR.