Developing highly efficient non-precious electrocatalytic materials for H-2 production in an alkaline medium is attractive on the front of green energy production. Herein, we successfully designed an electrocatalyst with superb hydrophilicity, high conductivity, and a kinetically beneficial structure using Ni2P/MXene over a 3D Ni foam (NF) for the alkaline hydrogen evolution reaction (HER) based on the laboratory and computational research works. The designed self-supported and highly effective electrocatalyst achieves a huge boost in the HER activity compared with that of pristine Ni2P nanosheets owing to the distinctive structure and synergy of coupling Ti3C2Tx and Ni2P. More specifically, Ni2P/Ti3C2Tx/NF produces an electric current density of 10 mA.cm(-2) under a low overpotential (135 mV) and shows excellent durability under alkaline (1 M KOH) conditions, and the observed performance degradation is negligible. The outstanding HER activity makes the synthetic strategy of Ni2P/Ti3C2Tx/NF a potential approach to be extended to other transition-metal-based electrocatalysts for enhanced catalytic performance.