Large quantities of environmentally toxic olive mill waste waters (OMWW) result from olive oil production worldwide. A synthetic water-soluble meso-tetra(2,6-dichloro-3-sulfonatophenyl)porphyrinate of iron(III) chloride (FePha) was used as biomimetic catalystto oxidatively couple toxic phenols in OMWW fractions obtained by micro-, ultra-, and nanofiltration, and reverse osmosis. The occurrence of oxidative coupling in different OMWW size-fractions was assessed by high performance size exclusion chromatography (HPSEC), before and after conformational disruption with acetic acid, and measurements of proton spin-lattice relaxation time in the rotating frame (T1(rho)H) through 13C-CPMAS-NMR spectroscopy. The concurrent reduction in toxicity of OMWW size-fractions brought about by the FePha treatment was monitored by an algal bioassay. HPSEC chromatograms of OMWW samples subjected to catalyzed coupling showed apparent weight-average molecular weight (Mwa) values varying from 18 to 185% larger than for control. Moreover, when such FePha-treated fractions were added to acetic acid prior to HPSEC, the Mwa values still ranged from 14 to 162% larger than for control fractions similarly treated with acetic acid. This evidence of polymerization among toxic phenols was confirmed by T1(rho)(H) values which were significantly enhanced by the FePha treatment, thereby indicating an increased conformational rigidity of OMWW materials. These molecular changes were reflected in a significantly reduced toxicity exerted on microalgae by the OMWW size-fractions subjected to catalyzed oxidative couplings. Our results suggest that OMWW can be effectively treated with a biomimetic catalyst to induce oxidative phenol polymerization and reduce their toxicity before amendments to soils or other disposal means.