The biosynthesis of the depsidone, fumarprotocetraric acid, a compound previously considered to be only produced by lichens, has been confirmed by using alginate-immobilized cells of Cladonia verticillaris. Immobilized cells only produce the depsidone when they are supplemented with FMN and acetate. This implies that fumaric acid which esterifies an alcohol function in the C3 of a depsidone precursor is added through a reducing, flavin-dependent, coupling reaction that uses the pool of succinyl-CoA from the fungal partner.