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Exploitation of efficient and stable photocatalyst for water splitting is pressing to solve the energy crisis. Four CdS@MoS2 nano‐heterojunctions were prepared by a single precursor thermal decomposition combined with one‐step hydrothermal method. The morphology of the prepared samples is spherical and has obvious core‐shell structure interface. The photocurrent of CdS@MoS2‐2 wt% is the largest, which is more over 40 times that of the pure CdS. In addition, CdS@MoS2‐2 wt% had superior photocatalytic H2 generation activity (20.23 mmol g−1 h−1) without any noble metal as a cocatalyst under visible light and show marked photocatalytic durability after a continuous test for 16 hours. This work provides a new insight for the design of core‐shell nano‐heterojunctions for other metal sulfide composites. [ABSTRACT FROM AUTHOR]