Antimony sulfide (Sb2S3) is widely used in photocatalysts and photovoltaic cells because of its abundant reserves, low toxicity, environmental friendliness, narrow band gap, and high light absorption capacity. Sb2S3 shows a quasi-one-dimensional structure composed of [Sb4S6]n nanoribbons, a lot of reported studies are focused on preparing Sb2S3 with [hk1] oriented dominant growth to improve the photogenerated carrier transport capacity of Sb2S3. However, there is relatively few research on the preparation of [hk1] oriented rod-like Sb2S3 by vapor transport deposition (VTD) method. In this work, the VTD method was used to prepare Sb2S3 with [hk1] oriented growth on the FTO substrate, and then composite with the ternary solid solution CdxZn1−xS. Finally, a novel Sb2S3/Cd0.6Zn0.4S S-scheme heterojunction with rod-like core-shell structure was successfully constructed, which could effectively improve the photoelectrochemical properties. Because the solid solution component x is adjustable, that is, CdxZn1−xS has continuously adjustable band gap width and energy level position, the Sb2S3/CdxZn1−xS heterojunction type can be regulated from Type-II to S-scheme. Photoelectrochemical (PEC) tests indicated that the composite photoanode Sb2S3/Cd0.6Zn0.4S achieved a higher photocurrent density (2.54 mA·cm−2, 1.23 V vs. RHE), which is about 4.31 times that of pure Sb2S3 nanorod photoanode (0.59 mA·cm−2, 1.23 V vs. RHE). © 2023 Elsevier B.V.