Two-dimensional layered transition metal dichalcogenides have emerged as promising materials for supercapacitors and hydrogen evolution reaction (HER) applications. Herein, the molybdenum sulfide (MoS2)@vanadium sulfide (VS2) and tungsten sulfide (WS2)@VS2 hybrid nano-architectures prepared via a facile one-step hydrothermal approach is reported. Hierarchical hybrids lead to rich exposed active edge sites, tuned porous nanopetals-decorated morphologies, and high intrinsic activity owing to the strong interfacial interaction between the two materials. Fabricated supercapacitors using MoS2@VS2 and WS2@VS2 electrodes exhibit high specific capacitances of 513 and 615 F g−1, respectively, at an applied current of 2.5 A g−1 by the three-electrode configuration. The asymmetric device fabricated using WS2@VS2 electrode exhibits a high specific capacitance of 222 F g−1 at an applied current of 2.5 A g−1 with the specific energy of 52 Wh kg−1 at a specific power of 1 kW kg−1. For HER, the WS2@VS2 catalyst shows noble characteristics with an overpotential of 56 mV to yield 10 mA cm−2, a Tafel slope of 39 mV dec−1, and an exchange current density of 1.73 mA cm−2. In addition, density functional theory calculations are used to evaluate the durable heterostructure formation and adsorption of hydrogen atom on the various accessible sites of MoS2@VS2 and WS2@VS2 heterostructures.