Owing to their high extinction coefficient and moderate band gap, cadmium chalcogenides are known as common semiconductors for photoelectric conversion. Nevertheless, no ideal cadmium chalcogenide with proper band structure is available yet for photoelectrochemical hydrogen evolution. In this work, we modified the band structure of CdTe via alloying with Se to achieve a ternary compound (CdSe0.8Te0.2) with n-type conduction, a narrower band gap, and a more negative band position compared to those of CdSe and CdTe. This novel material exhibits strong light absorption over a wider spectrum range and generates more vigorous electrons for hydrogen reduction. As a result, a photoelectrode based on nanoflake arrays of the new material could achieve a photocurrent density 2 times that of its CdSe counterpart, outperforming similar materials previously reported in the literature. Moreover, the quick transfer of holes achieved in the novel material was found to depress photocorrosion processes, which led to improved long-term working stability.