Developing highly efficient non-precious electrocatalytic materials for H2 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.