Photo-Fenton process was explored as photochemical pre-treatment to improve the biodegradability of a wastewater coming from a textile industry located in the south of France, which was characterized as very biorecalcitrant by means of Zahn–Wellens biodegradability test. The effect of H2O2, Fe(III) and temperature on the photo-mineralization processes have been studied and the optimal conditions were found. Experiments were made to obtain information concerning the evolution of the biodegradability of the treated effluent after 40 and 70% of photo-mineralization. The photo-treated effluent is not biocompatible and its complete mineralization cannot be performed by biological means. UV–VIS and high-performance liquid chromatography (HPLC) analyses show that aromatic intermediates remain in the effluent after the photo-treatment, which have been identified as the principal reason of the biorecalcitrance.