Vanadium Diselenide (VSe2) is a prominent candidate in the 2D transition metal dichalcogenides family for energy storage applications. Herein, we report the experimental and theoretical investigations on the effect of cobalt doping in 1T-VSe2. The energy storage performance in terms of specific capacitance, stability and energy and power density is studied. It is observed that 3% Co doped VSe2 exhibits better energy storage performance as compared to other concentrations, with a specific capacitance of 1/4193 F g-1 in a two-electrode symmetric configuration. First-principles Density Functional Theory based simulations support the experimental findings by suggesting an enhanced quantum capacitance value after the Co doping in the 1T-VSe2. By making use of the advantages of the specific electrode materials, a solid state asymmetric supercapacitor (SASC) is also assembled with MoS2 as the negative electrode. The assembled Co-VSe2//MoS2 SASC device shows excellent energy storage performance with a maximum energy density of 33.36 Wh kg-1 and a maximum power density of 5148 W kg-1 with a cyclic stability of 90% after 5000 galvano static charge discharge cycles. © 2022 IOP Publishing Ltd.