A chemical-bath deposition method has recently been applied for the industrial deposition of CdS buffer layers in high-efficiency Cu(In, Ga)Se 2 (CIGS) solar cells; however, its massive raw material waste and heavy pollution have also hindered its long-range industrialization. In this study, a type of low-pollution and controllable selective-area deposition of CdS thin films on cells was proposed and conducted by a photochemical deposition (PCD) technique using an aqueous solution containing S 2 O 3 2− , SO 3 2− , and Cd 2+ . The as-deposited films are low-crystallinity, uniform, and compact with thicknesses of 30−50 nm. Moreover, the depositions of CdS thin films were further investigated by tuning the deposition time, absorption of cadmium ions, sulfur concentration, and light intensity. Additionally, an ion-by-ion mechanism was proposed for the growth of CdS thin films by a PCD technique. Furthermore, the optimal CdS thin layer was applied in CIGS solar cells, which showed a high efficiency of 10.45%. This research would give new insight into the efficient deposition of CdS thin films on solar cells with low pollution.