MoS2 quantum dots (QDs)/CdS core/shell nanospheres with a hierarchical heterostructure have been prepared by a simple microwave hydrothermal method. The as-prepared samples are characterized by XRD, TEM, SEM, UV-VIS diffuse reflectance spectra (DRS) and N2-sorption in detail. The photocatalytic activities of the samples are evaluated by water splitting into hydrogen. Results show that the as-prepared MoS2 QDs/CdS core/shell nanospheres with a diameter of about 300 nm are composed of the shell of CdS nanorods and the core of MoS2 QDs. For the photocatalytic reaction, the samples exhibit a high stability of the photocatalytic activity and a much higher hydrogen evolution rate than the pure CdS, the composite prepared by a physical mixture, and the Pt-loaded CdS sample. In addition, the stability of CdS has also been greatly enhanced. The effect of the reaction time on the formations of nanospheres, the photoelectric properties and the photocatalytic activities of the samples has been investigated. Finally, a possible photocatalytic reaction process has also been proposed.