Display omitted •Nickel oxide with different particle sizes are developed by a facile process.•The smaller particle size of 6nm with face centered cubic structure was observed.•CV and EIS study shows the pseudocapacitive behavior of NiO nanostructures.•NiO with smaller particle size exhibited enhanced specific capacitance. In this work, we demonstrate the influence of nickel oxides with divergent particle sizes as the working electrodes for supercapacitor application. The nanostructured nickel oxide (NiO) is synthesized via facile sonochemical method, followed by calcination process. The crystallinity and surface purity of prepared samples are clearly examined by X-ray diffraction and Raman analysis. NiO crystallinity is significantly increased with increasing calcination temperatures. The surface analysis confirmed that the calcination at 250°C exhibited nanoclutser like NiO with average particle size of ∼6nm. While increasing the calcination temperature beyond 250°C, hexagonal shaped NiO is observed with enhanced particle sizes. The electrochemical performance confirmed the good redox behavior of NiO electrodes. Moreover, NiO with average particle size of ∼6nm exhibited high specific capacitance of 449F/g at a scan rate of 5mV/s compared to other samples with particle sizes of ∼21nm (323F/g) and ∼41nm (63F/g). This is due to the good ion transfer mechanism and effective electrochemical utilization of the working electrode.