Hexagonal perovskite YFeO 3 was synthesized by a complex-assisted sol-gel technique allowing crystallization at calcination temperatures below 700 • C. As determined by diffuse reflectance spectroscopy (DRS) and Tauc plots, the hexagonal YFeO 3 exhibits a lower optical band gap (1.81 eV) than the orthorhombic structure (about 2.1 eV or even higher) being typically obtained at elevated temperatures (>700 • C), and thus enables higher visible light photocatalysis activity. Structure and morphology of the synthesized YFeO 3 perovskites were analyzed by powder X-ray diffraction (XRD) and nitrogen adsorption, proving that significantly smaller crystallite sizes and higher surface areas are obtained for YFeO 3 with a hexagonal phase. The photocatalytic activity of the different YFeO 3 phases was deduced via the degradation of the model pollutants methyl orange and 4-chlorophenol. Experiments under illumination with light of different wavelengths, in the presence of different trapping elements, as well as photoelectrochemical tests allow conclusions regarding band positions of YFeO 3 and the photocatalytic degradation mechanism. X-ray photoelectron spectroscopy indicates that a very thin layer of Y 2 O 3 might support the photocatalysis by improving the separation of photogenerated charge carriers.