Fabricating the significant electrocatalysts with enriched activity and stability is necessary due to the increasing demands of the fuel cell industries for its commercialization. This report provides a widespread impact on fabrication of a suitable and significant porous bimetallic nanocatalyst for methanol oxidation reaction (MOR). Here, we have developed nanofoams of Cu-Co alloys/oxides with varied carbon supports using simple combustion method, where graphite oxide (GO) shows synergistic "catalyst-support" effect than other substrates. The morphological studies reveal a honeycomb-like structure with dense porous nature of Cu-Co nanofoam (CuCo@rGO). X-ray diffraction and spectroscopic studies reveal the formation of spinel structure of CuCo2O4 with active {110} facets in case of CuCo@rGO, exhibiting higher methanol electrooxidation activity of 198 mA/cm(2), which is found to be improved than that of the previous reports. The optimized composition, CuCo@rGO shows the slow decrease in the current in chronoamperometric studies with 40% retention of its activity even after 10 hours. The CoCu@rGO nanofoam shows improved Brunauer-Emmett-Teller surface area of similar to 50 m(2)/g due to the addition of GO. In addition, the composite shows an excellent electrochemical surface area value of 7.75 m(2)/g over other compositions of different carbon supports. The intrinsic effect of better conductivity of Co75Cu25@rGO has also been confirmed using impedance spectroscopy. The porous honeycomb structure of Co75Cu25@rGO composite synergistically impacts methanol oxidation and also forbids the formation of CO intermediate, maintaining the activity.