Wood-degrading basidiomycetes are some of the most effective bioconverters of lignocellulose in nature, however, the way in which they alter crystalline cellulose in wood at the molecular level is still not well understood. To face this, the objective of this review is to present some important characteristics of this type of fungi, to present some hypotheses regarding the mechanisms of degradation used: Specifically, we review the hypothesis of a system that uses the production of fungal chelators and their function in the chemistry of Fenton. This system will allow the production of hydroxyl radicals within the cell wall of the wood and partly mimics the action of brown rot fungi. In addition to this, biotechnological applications of some fungi that generate this type of rot are disclosed.