The reduction of molecular oxygen is considered to be a key reaction for electrochemical energy conversion in direct methanol fuel cells (DMFCs). The slow kinetics of oxygen reduction reaction along with the high cost of Pt catalyst hampers the application of fuel cells. In this study, we have reported for the first time oxygen reduction reaction (ORR) activity on rare earth cerium containing perovskite oxides composite with vulcan carbon (VC) in alkaline media. The study has demonstrated the synergistic role of vulcan carbon in cerium perovskite nanomaterials-VC composite for improving ORR activity. The 60 % CeCuO₃-VC perovskite oxide composite with surface areas of 180 m²/g showed better oxygen reduction capability as compared to that of bare cerium perovskite. On optimization, among all the prepared catalysts 60 % CeCuO₃-VC showed the highest ORR activity with low onset potential and high current density. Further, the optimized 60 %    CeCuO₃-VC followed the 4e^- pathway with 95 % methanol tolerance properties and high stability i.e 76 %. This study on cerium-based perovskite with vulcan carbon will provide an opportunity for the study of rare earth cerium perovskite electrocatalysts for electrochemical energy conversion.