A free-standing, 3D, macro/microstructured atomic-cobalt/cobalt-oxide–reduced-graphene-oxide (Co/Co3O4-Gr) composite has been developed for complete water splitting. The self-assembled porous morphology associated with the metal/metal oxide active sites makes the whole surface of the electrode conducive toward catalyzing hydrogen and oxygen evolution in alkaline media at a low onset potential. The liquid-crystal-mediated free-standing electrocatalyst shows oxygen evolution at the onset potential of 1.38 V and at the potential of 1.66 V for a current density of 10 mA cm−2. These potentials are comparable to the corresponding values for Ru/C (1.46 and 1.62 V, respectively). In addition, the promising hydrogen evolution performance of our composite compared to Pt/C in alkaline media makes it an efficient bifunctional electrocatalyst for comprehensive water splitting, as well as provides guidance for future electrochemical energy material technologies.