Colloidal core/shell heterostructured quantum dots (QDs) possessing quasi-type II band structure have demonstrated effective surface passivation and prolonged exciton lifetime, leading to enhanced charge separation/transfer efficiencies that are promising for photovoltaic device applications. Herein, we synthesized CuInS2 (CIS)/CdS core/shell heterostructured QDs and manipulated the optoelectronic properties via controlling the CdS shell thickness. The shell-thickness-dependent optical properties indicate the existence of a quasi-type II band structure in such core/shell QDs, which was verified by ultrafast spectroscopy and theoretical simulations. These quasi-type II core/shell QDs having various shell thicknesses are used as light absorbers for the fabrication of solar-driven QDs-based photoelectrochemical (PEC) devices, exhibiting an optimized photocurrent density of ∼6.0 mA/cm2 and excellent stability under simulated AM 1.5G solar illumination. The results demonstrate that quasi-type II CIS/CdS core/shell heterostructured QDs with tailored optoelectronic properties are promising to realize high-performance QDs-based solar energy conversion devices for the production of solar fuels.