A series of CdS with various shapes of microsphere, flower-like and leaf-like were template-freely synthesized by a hydrothermal method. Powder X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), scanning electron microscopy (SEM) and UV-vis absorption spectroscopy (UV-vis) were applied to characterize the morphology, optical and other physical properties of the as-prepared CdS. An optical spectrum analyzer was used to measure the wavelength of the illuminant on the slurry in the activity evaluations of photocatalytic reduction of CO2 over CdS. Both sources of cadmium and sulfur had great impact on the CdS morphology as can be seen in the SEM images. By means of a series of activity evaluations, the microspheric CdS made from cadmium nitrate and thioacetamide showed better photocatalytic activity for the reduction of CO2 to methyl formate (MF) in methanol than the flower-like and leaf-like CdS catalysts.