The photolysis and photo-catalysis of ferrioxalate in the presence of hydrogen peroxide with UV irradiation (UV/ferrioxalate/H2O2 process) for treating the commercial azo dye, reactive Black B (RBB), is examined. An effort is made to decolorize textile effluents at near neutral pH for suitable discharge of waste water. pH value, light source, type of initial catalyst (Fe3+ or Fe2+) and concentration of oxalic acid (Ox) strongly affected the RBB removal efficiency. The degradation rate of RBB increased as pH or the wavelength of light declined. The optimal molar ratio of oxalic acid to Fe(III) is three, and complete color removal is achieved at pH 5 in 2 h of the reaction. Applying oxalate in such a photo process increases both the RBB removal efficiency and the COD removal from 68% and 21% to 99.8% and 71%, respectively. (c) 2006 Elsevier B.V. All rights reserved.