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In this study, the polygonal structure of WO3 nanoparticles was constructed by the hydrothermal route, and the prepared materials were utilized for supercapacitor applications. The synthetic materials are WO3 nanoparticles in their monoclinic phase, according to the X-ray diffraction data. The morphologies of the WO3 samples are polygonal like and scanning electron microscope and transmission electron microscopy have confirmed it. To investigate the supercapacitance behavior of polygonal WO3, various techniques were used, such as galvanostatic charge–discharge, cyclic voltammetry, and electrochemical impedance spectroscopy (EIS). The polygonal WO3 nanoparticle modified on Ni-foam as a working electrode has a specific capacitance value of 870 F g−1 at 0.25 A g−1. The polygonal structure of WO3 nanoparticle-coated Ni-foam electrodes was very stable compared to other fabricated electrodes over the 10,000 cycles. The fabricated polygonal structure of the WO3 electrode has high capacitance retention (100.2%) and high coulombic efficiency (99%). The polygonal structure of WO3 makes it a particularly effective electrode material and a substantially better candidate for energy storage, especially supercapacitors. [ABSTRACT FROM AUTHOR]