Among three polymorphs of TiO2, the brookite is the least known phase in many aspects of its properties and photoactivities (especially comparable to anatase and rutile) because it is the rarest phase to be synthesized in the standard environment among the TiO2 polymorphs. In this study, we address the unrevealed photocatalytic properties of pure brookite TiO2 film as an environmental photocatalyst. Highly crystalline brookite nanostructures were synthesized on titanium foil using a well-designed hydrothermal reaction, without harmful precursors and selective etching of anatase, to afford pure brookite. The photocatalytic degradation of rhodamine B, tetramethylammonium chloride, and 4-chlorophenol on UV-illuminated pure brookite were invest...