Zinc sulfide (ZnS) was deposited onto the surface of mesoporous TiO2 film by a typical successive ionic layer adsorption and reaction (SILAR) process. By inducing a spontaneous cation exchange between ZnS and a target cation (Pb2+, Cu2+, Ag+, or Bi3+) dissolved in a chemical bath when they are in contact, it was demonstrated successfully that white translucent ZnS on the substrate could be changed to new brown-colored metal chalcogenides and the amount of ZnS deposited originally by different conditions could be compared in a qualitative way with the degree of color change. By utilizing this simple but effective process, the evolution of a well-known ZnS passivation layer prepared from different chemical baths in quantum dot (QD)-sensitized solar cells could be tracked visually by checking the degree of color change of TiO2/ZnS electrodes after the induced specific cation exchange. When applied to representative CdS QD-sensitized solar cells, it was revealed clearly how the different degrees and rates of ZnS deposition could affect the overall power conversion efficiency while finding an optimized passivation layer over TiO2/CdS electrode. An acetate anion-coupled Zn2+ source was observed to give a much faster deposition of a ZnS passivation layer than a nitrate anion one because of its higher pH-induced more-favorable adsorption of Zn2+ on the surface of TiO2. As another useful application of the ZnS-based cation exchange, as-deposited ZnS was used as a template for preparing a more complex metal chalcogenide onto a mesoporous TiO2 film. The ZnS-derived Sb2S3-sensitized electrode showed a promising initial result of over 1.0% overall power conversion efficiency with a very thin ZrO2 passivation layer between TiO2 and Sb2S3.