Systematically varied reaction times and concentrations of trifluoroacetic acid (TFA) have been used to remove polysaccharides associated with suberin isolated from potato wound periderm, thereby augmenting spectroscopic determinations of the molecular structure of this protective plant polyester. Treatments with dilute TFA left a residual insoluble material for which both solid-state 13C and 1H NMR spectra displayed significant improvements in resolution without compromising the integrity of the protective plant polyester, whereas higher concentrations of TFA made it possible to achieve controlled hydrolysis of the suberin aliphatic or aromatic domains. Among the isolated fragments were two hydroxyphenyl derivatives reported previously in lignins and a novel aliphatic-aromatic ester trimer that is identified provisionally. Together these protocols help to characterize the carbohydrate types that are bound covalently to the suberin polyester and to identify the interunit covalent linkages among the aliphatic ester, phenolic, and carbohydrate moieties in suberized potato tissue. The strategies described herein may also advance molecular-level investigations of lignocellulosic materials or vegetable tissues that exhibit strengthened intercellular adhesion.