Nano-forms of copper oxides (CuO and Cu2O) are potential candidates in the field of energy conversion and storage. Low temperature and controlled growth of three-dimensional nanostructured hierarchical assembly of CuO over Cu2O is reported here with demonstrated advantage in energy conversion and storage applications. Electrodeposited Cu2O is partially oxidized in an alkali bath to two different forms of hierarchical nanostructures (HNS): CuO/Cu2O and CuO:Cu(OH)2/Cu2O. Randomly oriented nanorods and nanoflakes with high surface area tussock-like nanostructure are formed during oxidation at room and at elevated temperatures, respectively. The nanoflake morphology exhibits a high surface area of 85.82 m2/g and sufficient ion percolation pathways, leading to an efficient electrode–electrolyte interface for electrochemical energy devices. A favorable conduction and valence band alignment in the HNS with respect to water redox level along with fast electron diffusion time of 0.8 μs make it an ideal photocathode.