The treatment of environmental pollution has become one of the most critical issues in the world. Despite the progress made in the study of semiconductor photocatalysis, it is still a challenge to obtain photocatalysts with high activity through relatively simple fabrication processes. In this work, monodisperse CdS spherical nanoparticles (SNPs) of various sizes and good crystallinity are obtained by only adjusting the starting ratio of reactants and the reaction temperature, exhibiting high photocatalytic performances. The photocatalytic rate constant of the ≈ 100 nm CdS SNPs, especially, is more than double that of P25. Furthermore, 3-mercaptopropyltrimethoxysilane is used to assist the interaction between ≈ 200 nm CdS SNPs and citrate-stabilized Au nanoparticles (NPs). The significant increase of photocatalytic activity is confirmed by the degradation of Rodamine B (RhB) under Xe light irradiation. At the optimal Au concentration (0.5 wt%), the prepared nanohybrids show the highest photocatalytic activity, exceeding that of pure CdS two times. The superior photocatalytic performances of the CdS SNPs-Au nanohybrids can be attributed to the intimate interfacial contact between CdS SNPs and Au NPs, which is a contributing factor to the improvement of transfer and the fate of photogenerated charge carriers from CdS SNPs to Au NPs.