 There is a continuous demand for non-precious and cost effective metal based electrocatalyst for carrying out Oxygen Reduction Reaction (ORR). In this paper, we have reported ORR performance of cerium oxide (CeO2) and volcano carbon (VC) composite varying volcano carbon percentage. CeO2/VC composite with different VC wt% was prepared by microwave mediated solvothermal method in just 10 min reaction time. Their electrocatalytic ORR activity was studied using Rotating Ring Disk Electrode (RRDE) technique in alkaline medium. The CeO2/VC (80 wt%) composite exhibited superior electrochemical stability and methanol tolerance capability as compared to Pt/C. Electrochemical Impedance Spectroscopy (EIS) study confirmed that in case of CeO2/VC composite, the synergistic interaction between VC and CeO2 leads to enhancement of ORR catalytic activity.