The detoxification process of waters contaminated with phenol, formaldehyde and phenol-formaldehyde mixtures was studied using advanced oxidation treatments (heterogeneous photocatalysis and Fenton), biological techniques (aerated biological and wetland reactors) and combinations of the two. It is shown that photocatalysis was efficient in the detoxification of concentrations below 50 mg L-1 of those compounds. Sample toxicity increased at higher concentrations due to the generated intermediates. Phenol-formaldehyde mixtures were impossible to detoxify by heterogeneous photocatalysis at any of the studied concentrations. Treatments using the Fenton reaction were able to degrade concentrations above 1000 mg L-1, though the use of a reagent such as peroxide makes it a costly technique. The efficiency of the biological aerated filter (BAF) mainly depended on initial concentration and toxicity, with removal rates of 3.08 and 0.26 g L-1 d(-1) obtained for phenol and formaldehyde, respectively. Taking into account the results obtained for the treatment of complex phenol-formaldehyde mixtures, the best combination of techniques for the treatment of concentrations found in the industrial wastewater studied in this paper was the Fenton + BAF technique which was able to detoxify phenol-formaldehyde concentrations (1:1) of 1000 mg L-1. (C) 2014 Elsevier B.V. All rights reserved.