Uniform, well-defined cadmium sulfide@cadmium selenide core/shell quantum dots (CdS@CdSe QDs) were, for the first time, successfully synthesized by a solvothermal method and chemical bath growth for photoelectrochemical activities. The as-synthesized CdS@CdSe QDs not only exhibit superior self-powered photoresponse behavior and excellent stability under ambient conditions but also display significantly improved current densities and photoresponsivity compared to those of individual CdS QDs or CdSe QDs, mainly due to the built-in electric field, and thus have great potential in the fields of renewable energy and renewable energy consumption for carbon neutrality target achievement.