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[Display omitted] • CdS@ZnO core–shell NRAs is constructed by ALD for H 2 evolution from PEC water splitting. • CdS@ZnO 200 presents an enhanced PEC H 2 evolution rate of 21.64 μmol·h−1·cm−2. • Z-scheme mechanism between CdS and ZnO promotes the separation of electrons and holes. • The close contact between two semiconductors reduces transfer resistance of charge carriers. • ZnO shell tightly wraps CdS core to prevent its photo-corrosion. Photoelectrochemical (PEC) water splitting provides a promising strategy for the production of clean hydrogen fuel. Herein, a new CdS@ZnO core–shell nanorod arrays (NRAs) is successfully constructed by atomic layer deposition (ALD) for H 2 evolution from PEC water splitting. The CdS@ZnO 200 obtained after 200 ALD cycles presents a significantly enhanced PEC H 2 evolution rate of 21.64 μmol·h−1·cm−2, which is about 9.4 times of pristine CdS NRAs (2.31 μmol·h−1·cm−2). The reasons for the improved PEC H 2 evolution performance can be ascribed to several aspects: firstly, the Z-scheme charge transfer mechanism formed between CdS core and ZnO shell promotes the effective spatial separation of photo-induced electrons and holes; secondly, the close contact between the two semiconductors resulted from ALD process helps to reduce the transfer resistance of charge carriers. In addition, the CdS core is tightly wrapped by ZnO shell, which helps to prevent the photo-corrosion of CdS core. This work provides a new type of photoanode material suitable for PEC H 2 evolution from water splitting, and provides an efficient anti-corrosion method for the use of photocorrosive semiconductor materials. [ABSTRACT FROM AUTHOR]