The brookite phase of TiO2 is hardly prepared and rarely studied in comparison with the common anatase and rutile phases. In addition, there exist immense controversies over the cognition of the light-induced liveliness of this material. Here, a novel, low-basicity solution chemistry method was first used to prepare homogeneous high-quality broolcite TiO2 single-crystalline nanosheets surrounded with four {210}, two {101}, and two {201} facets. These nanosheets exhibited outstanding activity toward the catalytic degradation of organic contaminants superior even to that of Degussa P25, due to the exposure of high-energy facets and the effective suppression of recombination rates of photo-generated electrons and holes by these facets as the oxidative and reductive sites. In contrast, irregularly faceted phase-pure brookite nanoflowers and nanospindles were inactive in catalytic reactions. These results demonstrate that the photocatalytic activity of brookite TiO2 is highly dependent upon its exposed facets, which offers a strategy for tuning the catalysts from inert to highly active through tailoring of the morphology and surface structure.