Rutile is the thermally most stable form of TiO₂, and can be produced at a high temperature, with a large number of photogenerated charge carriers on the oxide surface potentially available to reactants. However, rutile is seldom studied as a photocatalyst for organic oxidation, due to its poor ability for O₂ sorption and reduction in aqueous solution. Herein the effects of NaF and NaH₂PO₄ on rutile photocatalysis have been examined. For phenol degradation in aqueous solution, these anions were detrimental, with the trend contrary to those reported with anatase, brookite, and P25 (a mixture of anatase and rutile). After rutile was deposited with 0.5% Pt, however, these anions were beneficial, with the trend similar to those observed for a Pt-deposited anatase and P25. At the same amounts on Pt/rutile, interestingly, fluoride was approximately 3 times more active than phosphate, as observed for Pt/anatase. At a surface coverage higher than 90%, however, the positive effect of phosphate became smaller as its adsorption was increased. An independent measurement with a rutile film electrode showed that both fluoride and phosphate inhibited the adsorption and reduction of O₂, while they promoted the hole oxidation of phenol. A plausible mechanism is proposed, involving the fluoride-induced enhancement of bridged oxygen/hydroxyl radical formation and the hole oxidation of phosphate into the anion radicals.