A library of graphene-based hybrid materials was synthesized as novel hybrid electrochemical electrodes for electrochemical energy conversion and storage devices and electrocatalytical sensing namely enzymeless glucose sensing. The materials used were supercapacitive graphene-family nanomaterials (multilayer graphene-MLG; graphene oxide-GO, chemically reduced GO-rGO and electrochemical reduced GOErGO) and pseudocapacitive nanostructured transition metal oxides including cobalt oxide polymorphs (CoO and Co3O4) and cobalt nanoparticles (CoNP). These were combined through physisorption, electrodeposition, and hydrothermal syntheses approaches. This project was carried out to enhance electrochemical performance and to develop electrocatalytic platforms by tailoring structural properties and desired interfaces. Particularly, electrodeposition and hydrothermal synthesis facilitate chemically-bridged (covalently- and electrostatically- anchored) interfaces and molecular anchoring of the constituents with tunable properties, allowing faster ion transport and increased accessible surface area for ion adsorption. The surface morphology, structure, crystallinity, and lattice vibrations of the hybrid materials were assessed using electron microscopy (scanning and transmission) combined with energy dispersive spectroscopy and selected-area electron diffraction, X-ray diffraction, and micro-Raman Spectroscopy. The electrochemical properties of these electrodes were evaluated in terms of supercapacitor cathodes and enzymeless glucose sensing platforms in various operating modes. They include cyclic voltammetry (CV), ac electrochemical impedance spectroscopy, charging-discharging, and scanning electrochemical microscopy (SECM). These hybrid samples showed heterogeneous transport behavior determining diffusion coefficient (4⨯10-8 – 6⨯10-6 m2/s) following an increasing order of CoO/MLG < Co3O4/MLG < Co3O4/rGOHT < CoO/ErGO < CoNP/MLG and delivering the maximum specific capacitance 450 F/g for CoO/ErGO and Co3O4/ rGOHT. In agreement with CV properties, these electrodes showed the highest values of low-frequency capacitance and lowest charge-discharge response (0.38 s – 4 s), which were determined from impedance spectroscopy. Additionally, through circuit simulation of experimental impedance data, RC circuit elements were derived. SECM served to investigate electrode/electrolyte interfaces occurring at the solid/liquid interface operating in feedback probe approach and imaging modes while monitoring and mapping the redox probe (re)activity behavior. As expected, the hybrids showed an improved electroactivity as compared to the cobalt oxides by themselves, highlighting the importance of the graphene support. These improvements are facilitated through molecular/chemical bridges obtained by electrodeposition as compared with the physical deposition.