Exploring new strategies to design non-precious and efficient electrocatalysts can provide a solution for sluggish electrocatalytic kinetics and sustainable hydrogen energy. Transition metal selenides are potential contenders for bifunctional electrocatalysis owing to their unique layered structure, low band gap, and high intrinsic activities. However, insufficient access to active sites, lethargic water dissociation, and structural degradation of active materials during electrochemical reactions limit their activities, especially in alkaline media. In this article, we report a useful strategy to assemble vanadium diselenide (VSe2) into a 3D MXene/rGO-based sponge-like architecture (VSe2@G/MXe) using hydrothermal and freeze-drying approaches. The 3D hierarchical meso/macro-pore rich sponge-like morphology not only prevents aggregation of VSe2 nanosheets but also offers a kinetics-favorable framework and high robustness to the electrocatalyst. Synergistic coupling of VSe2 and a MXene/rGO matrix yields a heterostructure with a large specific surface area, high conductivity, and multi-dimensional anisotropic pore channels for uninterrupted mass transport and gas diffusion. Consequently, VSe2@G/MXe presented superior electrochemical activity for both the HER and OER compared to its counterparts (VSe2 and VSe2@G), in alkaline media. The overpotentials required to reach a cathodic and anodic current density of 10 mA cm-2 were 153 mV (Tafel slope = 84 mV dec-1) and 241 mV (Tafel slope = 87 mV dec-1), respectively. The Rct values at the open circuit voltage were as low as 9.1 Ω and 1.41 Ω for the HER and OER activity, respectively. Importantly, VSe2@G/MXe withstands a steady current output for a long 24 h operating time. Hence, this work presents a rational design for 3D microstructures with optimum characteristics for efficient bifunctional alkaline water-splitting.