Two-dimensional Bi 2 S 3 is considered a better photocatalyst when combined with CdS. To deeply understand electronic structures between CdS and Bi 2 S 3 , CdS@Bi 2 S 3 core−shell nanorods (NRs) were synthesized with a two-step hydrothermal method, and CdS@Bi 2 S 3 −MoS 2 composites were obtained with MoS 2 nanoparticles decorated on the surface of CdS@Bi 2 S 3 NRs. Then, the energy band alignments in CdS@Bi 2 S 3 −MoS 2 were constructed from XPS and UPS measurements, and dual z-scheme CdS@Bi 2 S 3 −MoS 2 heterostructures were confirmed from charge transfer with electron spin resonance (ESR) signals of •O 2 − and •OH. Finally, the photocatalytic hydrogen activities were carried out with the prepared samples. The results showed that the optimized CdS@Bi 2 S 3 core−shell NRs have a hydrogen production rate of 4.29 mmol•h −1 •g −1 , which is 8.4 times higher than that of the pure CdS nanorods, and the optimized CdS@Bi 2 S 3 −MoS 2 heterostructure has a hydrogen production rate of 8.72 mmol•h −1 •g −1 , which is 17 times higher than that of the pure CdS NRs. The enhanced photocatalytic activity can be ascribed to the dual z-scheme heterostructure and full-spectrum absorption; the former is favorable for the efficient separation of the photogenerated electron−hole pairs, and the latter is beneficial to the production of more photogenerated carriers. The studies will be helpful to understand the electronic structures of Bi 2 S 3 and the related heterostructures.