The development of hybrid structures in the form of an electrode for energy generation has an added advantage due to the synergistic functionality of two different components of electrode materials. It can be accomplished by the functionalization of the pristine electrode surface, hematite for instance with mesoscale elements such as Co3O4 results in the formation of Co3O4 flower like oriented aggregate (FLOA) in a small two pot hydrothermal solution deposition. These are formed in both the free standing form on an electronically conductive substrate such as fluorine doped tin oxide (A4) and in combination on top of Hematite (A3). This unique structure shows promising electrocatalytic performance in the presence of iron from Hematite and electrochemical stability. The morphology in A4 remains preserved even after 20- hour electrochemical operations while the morphology of hybrid counterpart (A3) transforms into dendritic microstructures after long- term electrochemical treatment (LTE). Both electrodes show a significant amount of hydrogen and oxygen evolution representing its water splitting capability with electrocatalytic effect. Also, electrocatalysts crystallographic structural development and compositional characteristics are studied. (C) 2017 The Electrochemical Society. All rights reserved.