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• 1–7 wt % Mo-doped NiO nanostructures are fabricated by using facile hydrothermal route. • Novel Mo-doped NiO nanowires (MoNi-5 NWs) have shown optimized electrochemical behavior. • First time as prepared Mo-doped NiO nanowires have shown a highest specific capacitance (1096.64F/g) and an excellent charge retention (80.95 %). • A good capacitance retention (79.7 % even after 3000 CV cycles) and ideal coulombic efficiency (92.20 %) is also delivered by these novel nanowires. To cope with energy crises occurred owe to over-consumption in the domain of industrial and domestic, researchers are focusing to design some efficient energy storage devices specially supercapacitors. Here, Mo-doped NiO nanowires based electrode material for supercapacitors have been fabricated. XRD, SEM, TEM, FTIR, BET and XPS studies revealed the successful growth and doping of molybdenum in nickel oxide. Their corresponding CV studies revealed that among the 1-7 wt% Mo-doped NiO nanomaterials, the 5 wt% Mo-doped NiO nanomaterial showed highest value of CV (1096.64 Fg−1). GCD studies showed an excellent change retention (80.95 %) and EIS exhibited highly conductive nature. The capacitance of 5 wt% Mo-doped NiO sample is 874.02 Fg−1 after 3000 cycles, which is 79.7% retention and coulombic efficiency at the end of 3000th cycle is 92.20%. On the basis of these above-mentioned abilities, this best sample is proposed to be used for practically application for supercapacitors. [ABSTRACT FROM AUTHOR]