The involvement of catechol and hydroxamate chelators, along with hydrogen peroxide and Fe3+, in the degradation of cellulosic and hemicellulosic substrates was examined with the purpose of improving our current knowledge of the non-enzymatic mechanisms involved in wood biodegradation by fungi. It could be demonstrated that a catechol chelator-mediated Fenton reaction not only clearly degraded hemicellulosic substrates but also significantly accelerated and increased the effectiveness of degradation reactions. On the other hand, when a hydroxamate chelator-mediated Fenton reaction was used, an inhibitory effect was observed. When cellulosic substrates underwent a chelator-mediated Fenton reaction, no significant difference in degradation was observed between catechol and hydroxamate chelator-mediated reactions. However, a catechol-mediated reaction did accelerate the degradation of cellulosic substrates at the beginning of reactions. In addition, it was observed that with a chelator-mediated Fenton reaction, oxidation of cellulose proceeds depolymerization. (c) 2005 Society of Chemical Industry.