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Antimony sulfide (Sb 2 S 3) 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. Sb 2 S 3 shows a quasi-one-dimensional structure composed of [Sb 4 S 6 ] n nanoribbons, a lot of reported studies are focused on preparing Sb 2 S 3 with [hk1] oriented dominant growth to improve the photogenerated carrier transport capacity of Sb 2 S 3. However, there is relatively few research on the preparation of [hk1] oriented rod-like Sb 2 S 3 by vapor transport deposition (VTD) method. In this work, the VTD method was used to prepare Sb 2 S 3 with [hk1] oriented growth on the FTO substrate, and then composite with the ternary solid solution Cd x Zn 1−x S. Finally, a novel Sb 2 S 3 /Cd 0.6 Zn 0.4 S 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, Cd x Zn 1−x S has continuously adjustable band gap width and energy level position, the Sb 2 S 3 /Cd x Zn 1−x S heterojunction type can be regulated from Type-II to S-scheme. Photoelectrochemical (PEC) tests indicated that the composite photoanode Sb 2 S 3 /Cd 0.6 Zn 0.4 S achieved a higher photocurrent density (2.54 mA·cm−2, 1.23 V vs. RHE), which is about 4.31 times that of pure Sb 2 S 3 nanorod photoanode (0.59 mA·cm−2, 1.23 V vs. RHE). • Rod-like Sb 2 S 3 with [hk1] orientation is deposited on FTO substrate by VTD method. • The Sb 2 S 3 /Cd x Zn 1−x S heterojunction type can be regulated from Type-Ⅱ to S-scheme. • The S-scheme heterojunction could effectively promote PEC water splitting. • The photoelectrode exhibits considerable photocurrent 2.54 mA·cm−2 at 1.23 V RHE. [ABSTRACT FROM AUTHOR]