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Suberin is a biopolymer present in some plant cell walls that modifies their biophysical properties. It contains both poly(phenolic) and poly(aliphatic) domains that are unique and distinct in both their chemical composition and tissue and sub-cellular location. The biosynthesis of the suberin poly(phenolic) domain is hypothesized to follow a peroxidase-mediated oxidative coupling process. In order for this to work, however, there has to be a peroxidase located at the site of suberin poly(phenolic) domain assembly, as well as a source of hydrogen peroxide to enable its function. This review focuses on the involvement of peroxidases in the macromolecular assembly of the poly(phenolic) domain of suberized tissues, with particular attention to the process in solanaceous plants, (where it has been most intensively studied), and addresses the question of the origin of the hydrogen peroxide essential to it.