Recently, the nanostructured nickel–cobalt bimetallic oxide (NiCo2O4) material with high electrochemical activity has received intensive attention. Beside this, the biomass assisted synthesis of NiCo2O4is gaining popularity due to its advantageous features such as being low cost, simplicity, minimal use of toxic chemicals, and environment-friendly and ecofriendly nature. The electrochemical activity of spinel NiCo2O4is associated with its mixed metal oxidation states. Therefore, much attention has been paid to the crystal quality, morphology and tunable surface chemistry of NiCo2O4nanostructures. In this study, we have used citrus lemon juice consisting of a variety of chemical compounds having the properties of a stabilizing agent, capping agent and chelating agent. Moreover, the presence of several acidic chemical compounds in citrus lemon juice changed the pH of the growth solution and consequently we observed surface modified and structural changes that were found to be very effective for the development of energy conversion and energy storage systems. These naturally occurring compounds in citrus lemon juice played a dynamic role in transforming the nanorod morphology of NiCo2O4into small and well-packed nanoparticles. Hence, the prepared NiCo2O4nanostructures exhibited a new surface-oriented nanoparticle morphology, high concentration of defects on the surface (especially oxygen vacancies), sufficient ionic diffusion and reaction of electrolytic ions, enhanced electrical conductivity, and favorable reaction kinetics at the interface. The electrocatalytic properties of the NiCo2O4nanostructures were studied in oxygen evolution reaction (OER) at a low overpotential of 250 mV for 10 mA cm−2, Tafel slope of 98 mV dec−1, and durability of 40 h. Moreover, an asymmetric supercapacitor was produced and the obtained results indicated a high specific capacitance of (Cs) of 1519.19 F g−1, and energy density of 33.08 W h kg−1at 0.8 A g−1. The enhanced electrochemical performance could be attributed to the favorable structural changes, surface modification, and surface crystal facet exposure due to the use of citrus lemon juice. The proposed method of transformation of nanorod to nanoparticles could be used for the design of a new generation of efficient electrocatalyst materials for energy storage and conversion uses.