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Quantum dots (QDs) are attractive systems for potential applications in future solar energy technologies, due to their optical properties which are tunable as a function of size and composition. In this study, we synthesized PbS QDs with first excitonic peak in the range 1060 to 1300 nm using a PbCl 2 /sulfur molar ratio of 10:1. The first excitonic absorption peak from 1300 to 950 nm of the PbS/CdS core/shell QDs can be further synthesized via the cation exchange approach. Our method resulted in high quantum yield, good stability, monodisperse QD solutions with a full surface coverage by excess Cd cations. In addition, we used our core/shell QDs in a photoelectrochemical cell for hydrogen generation. This heterostructure exhibited a saturated photocurrent as high as 3.3 mA cm -2 , leading to ∼29 ml cm -2 d -1 hydrogen generation, indicating the strong potential of our core/shell QDs for applications in water splitting.