It is still debatable whether the photocatalytic oxidation of cyanide proceeds via hydroxyl radicals or by photogenerated holes. We synthesized pure TiO₂ catalysts via sol-gel process. In order to elucidate the oxidation pathway of cyanide, we used hydroxyl radical scavengers and controlled the concentration of surface hydroxyl group on the catalysts adopting fluoride-exchange. The degree of fluoride-exchange of TiO₂ catalysts was independent of the pH of suspension. We also adopted a polyoxometalate, tungstophosphoric acid (TPA, H₃PW₁₂O₄₀) which is well known for high charge transfer ability and hydrolytic stability. TPA-modified TiO₂ catalysts were prepared with solgel technique to overcome the high solubility of TPA in water. As another attempt for the insoluble TPA, proton of TPA supported on TiO₂ catalysts was replaced by cesium ion to form Cs-TPA/TiO₂ catalysts. Both attempts were successful in immobilizing TPA on TiO₂ catalysts. Commercially available TiO₂ catalysts such as P25 from Degussa AG were also used as catalysts. XRD analysis revealed that pure TiO₂ and TPA-modified TiO₂ catalysts prepared by sol-gel process were composed of well-developed anatase crystalline structure. In the presence of hydroxyl radical scavengers, the photoactivity of TPA-modified TiO₂ catalysts was retarded much less than that of pure TiO₂ catalysts. The concentration of surface hydroxyl group was effectively suppressed by the fluoride-exchange causing the decrease of the activity of the catalysts. In the case of fluoride-exchanged catalysts, the drop in activity was obvious for the pure TiO₂ catalysts in the presence of iodide as a hydroxyl radical scavenger suggesting that indirect oxidation via hydroxyl radicals was the preferential reaction pathway. For the TPA-modified TiO₂ catalysts, meanwhile, the diminution was such a small extent suggesting that direct oxidation by photogenerated holes was the main reaction pathway. The activity arising from TPA in the catalysts was due to the Keggin structured anion (PW₁₂O₄₀^3-) which acted as an electron relay with the aid of dissolved oxygen in the reaction system.