Photoelectrochemical (PEC) hydrogen generation based on colloidal quantum dots (QDs) is very promising because of its high solar energy to fuel conversion efficiency and low fabrication costs. However, its commercial development is hindered by various challenges, including the widespread use of toxic heavy metal–based QDs as sensitizers. We report an environmentally friendly, high efficiency PEC device in which the photoanode consists of a mesoporous TiO₂ film sensitized with heavy metal-free, near-infrared (NIR) colloidal CuInSe_xS_2−x (CISeS) QDs. To reduce surface-related traps, we grew an ultrathin ZnS shell on the CISeS core QDs by cation exchange. The PEC cell based on this core/shell CISeS/ZnS QDs exhibits suppressed charge recombination and a saturated photocurrent density of ~5.3 mA/cm² under one sun illumination (AM 1.5 G, 100 mW/cm²). In addition, the as-prepared PEC device shows an outstanding stability, exhibiting a drop of only 23% after 9 h illumination. The success in using such core/shell CISeS/ZnS QDs paves the way to realize environment-friendly, high efficiency and cost-effective PEC devices for hydrogen production.