Novel flake-like Ni1−xSnxO2 particles were successfully prepared by template-free hydrothermal synthesis. The prepared samples were investigated for their properties by different characterization techniques. Scanning micrographs showed that the obtained particles consisted of nanoflakes. The X-ray diffraction results of the Ni1−xSnxO2 revealed the formation of mixed-phase Ni/SnO2 having the typical tetragonal structure of SnO2, and the cubic structure of Ni in a nanocrystalline nature. The doping with Ni had a certain influence on the host’s lattice structure of SnO2 at different doping concentrations. Confirmation of the functional groups and the elements in the nanomaterials was accomplished using FTIR and EDS analyses. The electrochemical performance analysis of the prepared nanomaterials were carried out with the help of the CV, GCD, and EIS techniques. The specific capacitance of the synthesized nanomaterials with different concentrations of Ni dopant in SnO2 was analyzed at different scanning rates. Interestingly, a 5% Ni-doped SnO2 nanocomposite exhibited a maximum specific capacitance of 841.85 F g−1 at 5 mV s−1 in a 6 M KOH electrolyte. Further, to boost the electrochemical performance, a redox additive electrolyte was utilized, which exhibited a maximum specific capacitance of 2130.33 at 5 mV s−1 and an excellent capacitance retention of 93.22% after 10,000 GCD cycles. These excellent electrochemical characteristics suggest that the Ni/SnO2 nanocomposite could be utilized as an electrode material for high-performance supercapacitors.