Monodisperse CdS nanospheres assembled by small nanoparticles were prepared using dimethyl sulfoxide (DMSO) as a solvent through several routes including thermolysis of xanthate, the reaction of cadmium acetate (Cd(CH3CO2)(2)) with thiourea, and interfacial reaction of CS2 and Cd(CH3-CO2) 2/DMSO. The corresponding products possessed the particle sizes ranging from around 35 to 45 nm, 63 to 73 nm, and 240 to 280 nm, respectively. These products presented uniform spherical morphology, which provide insights into the effect of DMSO on CdS morphology. DMSO, as an aprotic and polar solvent, possesses unique properties. The oxygen and sulfur atoms in DMSO can coordinate to metal ions on nanoparticles surface, and the high polarity of DMSO is favorable to fast reaction, nucleation, growth, and Ostwald ripening, forming monodisperse nanospheres with narrow size distribution. The influence of CdS size on its photocatalytic activity was evaluated using Rhodamine B (RhB) as a model compound under visible light irradiation.