This work reports an in-situ, one-step hydrothermal preparation procedure of a binder-free electrode growth of Ni6Se5on nickel foam (Ni6Se5/NF) with a rod-like structure. Ni6Se5is an enveloped transition metal chalcogenides of formula M(n+1)Xn(where 2≤n≤8, M is a transition metal and X is chalcogen) of the nickel selenide family. The Ni6Se5/NF electrode described here demonstrates an exceptional lifetime of 81% capacitance retention over 20000 cycles and a high specific capacitance of 473.5 Fg-1at a current density of 4 Ag-1. The Ni6Se5/NF/activated carbon asymmetric supercapacitor exhibits a remarkable 97.3 Whkg-1energy density and a 2325 Wkg-1power density. Ni6Se5served as an active electrode material in supercapacitor applications and offered exceptional power density and long cycle life. Ni6Se5/NF, used as an anode for Li-ion batteries (LIB), has a lithium storage capacity of 939.7 mAhg-1at 100 mAg-1current density. Ni6Se5active electrode material's excellent energy storage capability, which was previously unreported, is particularly beneficial for electrochemical energy storage device applications.