Flower-like BiOBr sub-microstructures about 500 nm in diameter have been synthesized in the presence of tetraethylammonium bromide (TEAB) via a solution route at room temperature. SEM observation shows that these sub-microflowers are composed of nanoflakes with the thickness of 20 nm. The photocatalytic activities of flower-like BiOBr were evaluated by the degradation of methyl orange (MO) and phenol under visible-light and UV-light irradiation, which presented the efficiencies up to 97% within 1.5 h and 45% within 4 h, respectively.