Colloidal quantum dots (QDs) are promising building blocks towards the development of cost-effective and high-efficiency photoelectrochemical (PEC) cells. Unfortunately, the frequent use of QDs possessing heavy metals (e.g. Cd and Pb) in state-of-the-art QD-based PEC technologies is a major obstacle regarding their future commercial perspective. In this work, we synthesized heavy metal-free quaternary CuZnInS₃ (CZIS) with variable Cu : Zn ratios and fabricated corresponding QDs-PEC devices via a facile chemical bath deposition (CBD) technique. It is revealed that the tuned CZIS (1Zn) QDs (i.e. Cu : Zn ratio of 1 : 1) can result in optimized optical properties including enhanced quantum yield, suppressed nonradiative recombination and extended excitonic lifetime. Accordingly, as-fabricated CZIS (1Zn) QD-based photoanodes demonstrated increased charge transfer rate and decreased electron transport resistance for improved PEC performance. The results indicate that tuning the composition of heavy metal-free multinary QDs is one of the promising pathways to achieve eco-friendly and high-performance PEC systems for solar hydrogen production.