Photocatalytic hydrogen evolution reaction is one of the remarkable methods to produce clean and renewable fuel. However, the application of photocatalysts is still restricted because of the high recombination rate of photo-excited carriers and low photocatalytic activity. Herein, one-dimensional shell-core Schottky junction NiO@Cd0·75Zn0·25S composite nanorods have been synthesized successfully by self-assembly growing on the surface of Cd0·75Zn0·25S (CZS) nanorods with rich sulfur vacancies. The improved photocatalyst NiO@Cd0·75Zn0·25S sample (CN-0.15) exhibits a highly efficient photocatalytic hydrogen evolution rate of 745.41 μmol h−1 with 5 mg photocatalyst (corresponding to 149.1 mmol g−1 h−1) and apparent quantum efficiency (AQE) 12.5% at 420 nm, which is 5 times higher than that of pure CZS. Series results of characterizations and density functional theory (DFT) calculation provide a novel strategy for constructing Schottky junction by multi-step interfacial and defect engineering for H2 evolution.