The development of efficient non-precious metal electrocatalysts through more economical and safe methods is consistent with the goals of sustainable development and accelerating the achievement of “carbon neutrality” in the 21st century but remains potentially challenging. Mott–Schottky heterojunction interfaces generated from metal/semiconductor have been a hot topic of recent research because of the unique built-in electric field effect which allows the preparation of more superior catalysts for water electrolysis. Herein, a glutinous rice potpourri-like Mott–Schottky two-dimensional (2D) nanosheet (abbreviated as Ni/CeO2 HJ-NSs) electrocatalyst composed of metal nickel (Ni) and cerium oxide (CeO2) hetero-nanoparticles was synthesized by a simple and scalable self-assembly and thermal reduction strategy. The experimental results and mechanistic analysis show that the Mott–Schottky heterojunction interface composed of metallic Ni and n-type semiconductor CeO2 with built-in electric field induces the electron redistribution at the interface to accelerate the dissociation of water and the binding of reaction intermediates, thus achieving lower water dissociation energy and more thermoneutral ΔGH* value to expedite the kinetics of the hydrogen evolution reaction (HER). Thus, the prepared Ni/CeO2 HJ-NSs exhibit excellent HER catalytic performance in 1 M KOH electrolyte with an overpotential of only 72 mV at 10 mA cm−2, as well as a moderate Tafel slope of 65 mV dec−1 and an extraordinary long-term stability over 50 h, laying a solid foundation for further in-depth investigation. The synthesis of splendid electrocatalysts by exploiting the metal/semiconductor interface effect provides an innovative way for the future generation of Mott–Schottky-based heterostructures with three or more heterocompositions with two or more heterojunction interfaces.