This study assessed the applicability of a ferrous oxalate mediated photo-Fenton pretreatment for indigo-dyed wastewaters as to produce a biodegradable enough effluent, likely of being derived to conventional biological processes. The photochemical treatment was performed with ferrous oxalate and hydrogen peroxide in a Compound Parabolic Concentrator (CPC) under batch operation conditions. The reaction was studied at natural pH conditions (5-6) with indigo concentrations in the range of 6.67-33.33 mg L-1, using a fixed oxalate-to-iron mass ratio (C2O42-/Fe2+ = 35) and assessing the system's biodegradability at low (257 mg L-1) and high (1280 mg L-1) H2O2 concentrations. In order to seek the optimal conditions for the treatment of indigo dyed wastewaters, an experimental design consisting in a statistical surface response approach was carried out. This analysis revealed that the best removal efficiencies for Total Organic Carbon (TOC) were obtained for low peroxide doses. In general it was observed that after 20 kJ L-1, almost every treated effluent increased its biodegradability from a BOD5/COD value of 0.4. This increase in the biodegradability was confirmed by the presence of short chain carboxylic acids as intermediate products and by the mineralization of organic nitrogen into nitrate. Finally, an overall decrease in the LC50 for Artemia sauna indicated a successful detoxification of the effluent. (C) 2012 Elsevier B.V. All rights reserved.