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CdS@ZnS core shell nanocomposites were prepared by a one-pot hydrothermal route. The morphology of the composite was tuned by simply changing the Zn²⁺ precursor concentration. To characterize the samples prepared, various techniques were employed, including XRD, FESEM, TEM, XPS and UV-vis DRS. The band gaps of CdS and ZnS were measured to be 2.26 and 3.32 eV, respectively. Compared with pure CdS, the CdS@ZnS samples exhibited a slight blue shift, which indicated an increased band gap of 2.29 eV. The CdS@ZnS core shell composites exhibited efficient photocatalytic performance for H₂ generation under simulated sunlight illumination in contrast to pure CdS and ZnS. Additionally, an optimized H₂ generation rate (14.44 mmol·h⁻¹·g⁻¹_cat) was acquired at CdS@ZnS-2, which was approximately 4.6 times greater than that of pure CdS (3.12 mmol·h⁻¹·g⁻¹_cat). Moreover, CdS@ZnS heterojunction also showed good photocatalytic stability. The process of charge separation over the photocatalysts was investigated using photoelectrochemical analysis. The findings indicate that the CdS@ZnS nanocomposite has efficient charge separation efficiency. The higher H₂ generation activity and stability for CdS@ZnS photocatalysts can be attributed to the intimate interface in the CdS@ZnS core–shell structure, which promoted the light absorption intensity and photoinduced charge separation efficiency. It is expected that this study will offer valuable insights into the development of efficient core shell composite photocatalysts.