The development of pH-versatile, high-performing, and durable catalysts for hydrogen evolution reaction (HER) is crucial to satisfy the complex environment of water electrolysis industry. Herein, we present the synthesis of a hierarchical multiphase heterointerfaces Ni2P–CoP/MoO2 nanocatalyst with exceptionally high HER activity in the entire pH range through a facile three-step process involved hydrothermal, electrodeposition, and in situ phosphating treatment. Experiments and characterization revealed the strong electronic interactions among the phases of Ni2P, CoP, and MoO2, which endowed the Ni2P–CoP/MoO2 with high hydrogen evolution activity in different pH ranges. Meanwhile, the layered structure of our as-prepared catalyst makes the massive exposure of active sites. As a result, the Ni2P–CoP/MoO2 catalyst shows remarkable performance, requiring mere overpotentials of 33, 41, and 23 mV to drive 10 mA cm−2 in 1 M KOH, 1 M phosphate buffer solution, 0.5 M H2SO4, respectively. Moreover, the catalyst exhibits excellent stability in the chronopotentialmetry test under different pH electrolyte. Impressively, the Ni2P–CoP/MoO2 catalyst coupled with Ni–Fe LDH to form an overall water splitting system only require 1.50 V to drive 10 mA cm−2. Furthermore, this system actuated by wind and solar energy can stably undergo a continuous production of hydrogen and oxygen.