In this study, the biphase effect of brookite with anatase or rutile has been reinvestigated by using phenol degradation in aqueous solution as a model reaction. Prior to use, each oxide was sintered at 500 °C. Then two oxides were mixed in alcohol, followed by drying and sintering at 450 °C. Solid characterization showed that each oxide remained intact, in terms of the average crystallite size and surface area. As the weight percent of anatase or rutile in the mixture increased, the apparent activity of TiO₂ for phenol degradation under O₂ increased, and then decreased. A maximum apparent activity of TiO₂ was observed at 50% of anatase and rutile, respectively. However, with the same amount of silver ions on the oxide surface for phenol degradation under N₂, the intrinsic activity of TiO₂ became independent of the content of either anatase or rutile. These observations indicate that the thermodynamically possible charge transfer between two phases does not occur in practice. Moreover, for the photocatalytic reduction of O₂ to H₂O₂ in an aqueous suspension containing excess phenol, anatase was more active than brookite, followed by rutile. Accordingly, it is proposed that there is an interfacial O₂ transfer from anatase to brookite, and/or from brookite to rutile. This would improve the efficiency of the charge separation and consequently increase the rate of phenol degradation at interfaces.