Defect engineering in reduced graphene oxide (rGO) for a smart design of fuel-cell supports has become an effective approach to improve the restricted two-dimensional (2D) mass and charge transfer and to boost the alcohol oxidation reaction. The present minireview describes recent trends across prominent characteristics of tailored reduced graphene oxides, which include but are not restricted to, engineered three-dimensional (3D) nanostructures for better mass transport, tuned electron/hole conduction for easier electrical transport, and hybridized surfaces for high electrocatalytic activity. Special focus fixes upon the experimental progress on defect engineering, from three-dimensional structure assembly to surface metal complexation and heteroatom doping to size-controlled defect formation. Given their crucial impact on reduced graphene oxide properties, controlled methods for synthesis, and processing offer considerable promise toward next-generation carbon nanomaterials for electrocatalysis.