The hierarchical structures of nanosheets, micro-roses and micro-woolen like CuO nanosheets were directly fabricated on stainless steel via surfactant-free and inexpensive chemical bath deposition (CBD) method. Further, these CuO nanostructures demonstrate excellent surface properties like uniform surface morphology, high surface area and uniform pore size distribution of CuO samples. The electrochemical properties of CuO nanostructures have been investigated by cyclic voltammetry, charge–discharge and electrochemical impedance spectroscopy techniques. The electrochemical studies of the CuO samples show obvious influence of surface properties on the pseudocapacitance performance. The maximum specific capacitances of nanosheets, micro-roses and micro-woolen like CuO nanosheets are found to be 303 Fg− 1, 279 Fg− 1 and 346 Fg− 1, respectively at 5 mV s− 1 scan rate. Further, the EIS analysis shows lower ESR value, high power performance, excellent rate as well as frequency response of micro-woolen like CuO sample. The Ragone plot ascertains better power and energy densities of all three CuO nanostructured samples than other electrical energy storage devices. The long-term cycling performance of CuO is examined at different scan rates and the morphology changes of the electrode materials were studied. Present investigation suggests the inexpensive CBD approach for fine-tuning surface properties of oxide materials for energy storage applications.