This study addresses the pre-treatment of toxic and recalcitrant compounds found in the waste waters arriving at a treating station for industrial effluents containing chlorinated aromatics and non-aromatic compounds, anilines, phenols, methyl-tert-butyl-ether (MTBE). By reducing the total organic carbon (TOC) of these waste waters the hydraulic load for the further bacterial processing in the secondary biological treatment is decreased. The TOC decrease and discoloration of the waste waters was observed only under light irradiation in the reactor by immobilized Fenton processes on Fe/C-fabrics but not in the dark. The energy of activation for the degradation of the waste waters was of 4.2 kcal/mol. The degradation of the waste waters was studied in the reactor as a function of (a) the amount of oxidant used (H2O2), (b) the recirculation rate, (c) the solution pH and (d) the applied temperature. With these parameters taken as input factors, statistical modeling allows one to estimate the most economic use of the oxidant and electrical energy to degrade these waste waters. The concentration of the most abundant organic pollutants during waste waters degradation was followed by gas chromatography/mass spectrometry (GC-MS). The ratio of the biological oxygen demand to the total organic carbon BOD5/TOC increased significantly due to the Fe/C-fabric catalyzed treatment from an initial value of 2.03 to 2.71 (2 h). The reactor results show that the recirculation rate has no influence on the TOC decrease of the treated waters but affects the BOD increase of these solutions.