We herein present a structure consisting of two-dimensional (2D) single-crystal Ni3S2 nanosheets designed on one-dimensional (1D) Ni3S2 nanoprism arrays (also known as Ni3S2 nanoprism@nanosheets). These arrays are directly synthesized over nickel foam, which is referred to as Ni3S2/NF. These structures can be used as binderless, self-supporting electrodes for bifunctional methanol oxidation reaction (MOR) applications and high energy density hybrid supercapacitors (HSC). Ni3S2/NF is synthesized through the two steps of hydrothermal processes. In step I, 1D hexagonal Versailles Santa Barbara-5 (VSB-5) nanorod arrays have been prepared onto the surface of NF (denoted as VSB-5/NF). The precursor for step II was 1D VSB-5 nanorod arrays, which were transformed into Ni3S2 using Na2S as a sulfur source via the Kirkendall effect. Electrochemical examination results show that as-synthesized Ni3S2/NF electrode exhibited a high specific capacitance (Cs) of 145.0 mA h g−1 at 5 A g−1, low series resistance (0.18 Ω) and charge-transfer resistance (0.05 Ω), small relaxation time constant (τ0 = 8 ms) and high frequency response at 125.8 Hz. Ni3S2/NF has a superior specific capacity of 145.0 mA h g−1 at 5 A g−1 as a SC electrode. The Ni3S2/NF//CNTs/NF HSC can be operated up to 1.6 V in a 3 M KOH electrolyte, delivering an impressive energy density of 256.35 W h kg−1 at a power density of 6400 W kg−1. The as-assembled Ni3S2/NF//CNTs/NF HSC device exhibited an impressive stability of 81 % even after undergoing 10,000 charge-discharge cycles. When compared to previously reported catalysts, Ni3S2/NF was proved to be an excellent electrocatalyst for MOR due to its ability to generate a current density of 215.0 mA cm−2 at 0.5 VSCE, while maintaining a superior and stable current density of 619.2 mA cm−2 at 0.8 VSCE.