Regular shape and size regularity of quantum dots (QDs) significantly influence the photoelectrical properties of solar photoelectrochemical (PEC) cells. Two types of green Cu2SnS3 (CTS) QDs, sphere-like and bullet-like, were synthesized via the hot injection method by modulating the ratio of sulfur precursors. Compared with bullet-like CTS QDs, sphere-like CTS QDs exhibit a more negative conduction-band minimum and a narrower bandgap, enhancing sunlight absorption and utilization efficiency. These QDs were deposited onto TiO2 nanorod arrays individually to form p–n heterojunction photoanodes, which were assembled into PEC cells with Pt-plate counter electrodes for water-splitting H2 production. The experimental results demonstrate that the sphere-like CTS/TiO2 photoanode exhibits excellent PEC performance due to its more systematical spherical structure and homogeneous size distribution, achieving a photocurrent density of 2.54 mA cm−2, a hydrogen production yield of 162.1 μmol cm−2 within 4-hour illumination (AM 1.5G, 100 mW cm−2), and, especially, long-term high stability of hydrogen production for 16 consecutive hours. The enhanced performance of the sphere-like CTS/TiO2 photoanode is attributed to its superior photoabsorption, shorter charge-carrier diffusion length and improved charge-separation efficiency. By modulating the morphology and size uniformity of CTS QDs as photosensitizers, this work demonstrates a viable strategy to boost the charge separation kinetics and light-harvesting capacity of PEC systems, thereby achieving efficient solar-to-hydrogen conversion.