Efficient separation of photo-generated electrons and holes is crucial for improving the photocatalytic activity of semiconductor photocatalysts. In the present study, we show surface heterojunction is existed on anatase TiO2 with exposed {101}, {010}, {001}, and {110} facets. With the help of selective Pt deposition, it is found the Schottky junction together with proper surface heterojunction is helpful to separate the photo-generated electrons and holes. Moreover, the photo-reduction and photo-oxidation activities of the facets are depended on the reaction systems, resulting in self-adjusted surface heterojunction. The as-prepared photocatalyst will give the highest phenol degradation efficiency when Pt nanoparticles are only deposited on the {101} and {010} facets. In contrast, more Pt deposited on the {001} and {110} facets will decrease the photocatalytic activity. The average phenol degradation rate, which will gradually reduce along with the increased phenol concentration, of TiO2 (20 mg) is ca. 1.59 mg/min when its concentration is lower than 8 mg/L. However, similar results have not been observed in P25-based reaction systems, evidencing the great influence of self-adjusted surface heterojunction. This study may be helpful to understand the photocatalytic mechanisms of semiconductor photocatalysts with exposed different facets. Thus more efficient practical application of the photocatalysts for environment protection can be reached.