Large-scale, highly crystalline, high surface area carbon nanospheres (CNSs; similar to 250 nm) were synthesized on Cu substrate by optimized two step chemical vapor deposition (CVD) approach from a mixture of camphor and naphthalene as a source of carbon at 950 degrees C using Ar as a carrier gas. On the basis of host of characterization techniques the mechanistic pathway proposed for the formation of CNSs having ordered graphite crystal structure. The present approach is capable of producing monodispersed, high yield and ultra-high purity (no other carbon impurities) nanospheres. This work further report on the electrocatalytic performance of as synthesized CNSs and acid treated CNSs for the ascorbic acid (AA) oxidation reaction as a model reaction for direct oxidation fuel cells. These CNSs based electrocatalytic systems exhibits enhanced current densities and lower oxidation overvoltages response, demonstrating excellent catalytic activities towards AA oxidation could be due to their advantageous structural features.