Abstract The optical absorption edge of brookite TiO2 was measured at room temperature, using natural crystals. The measurements extend up to 3.54 eV in photon energy and 2000 cm−1 in absorption coefficient. The observed absorption edge is broad and extends throughout the visible, quite different from the steep edges of rutile and anatase. No evidence of a direct gap is seen in the range measured. The spectral dependence of the absorption strongly suggests that the brookite form of TiO2 is an indirect-gap semiconductor with a bandgap of about 1.9 eV.