Improving the stability and efficiency of non-noble metal based ORR (oxygen reduction reaction) electrocatalyst is crucial for the commercialization of fuel cell technology. Here, we report the synthesis of cobalt-polyoxometalate nanocomposite with carbon (CoP@C) by greener strategy, which shows an interesting enhancement in the kinetics of oxygen electroreduction process. The CoP@C nanocomposite exhibited improved catalytic activity toward ORR with E-onset 1.00 V vs RHE and current density of 4.2 mA/cm(2) at 1600 rpm in alkaline condition. Further, CoP@C electrocatalyst showed a single step similar to 4 electron transfer pathway, high tolerance to methanol, and exhibited superior stability compared with 20 wt% Pt/C. Thus, CoP@C could be a cheaper and potential candidate for ORR electrocatalysis in fuel cells. The superiority of the catalyst in terms of activity and durability arises due to the uniform distribution of cobalt-polyoxometalate nanoclusters on carbon surface and the synergetic effect of POM, cobalt, and carbon.