Crude protein extracts from the chickpea (Cicer arietinum L.) pathogenic fungus Ascochyta rabiei catalyze the NADPH dependent conversion of the pterocarpan phytoalexins medicarpin and maackiain to 1) 2′-hydroxyisoflavans, 2) 1 a-hydroxypterocarp-1,4-diene-3-one, and 3) 10,2′-dihydroxyisoflav-8-ene-7-one derivatives. A pterocarpan : NADPH oxidoreductase which cleaves the benzylphenyl ether bond of the phytoalexins was purified some 100-fold and partially characterized with regard to its kinetic properties. The oxidoreductase was shown to be specific for NADPH and 3-hydroxypterocarpans. The enzyme appears to be constitutively expressed by A. rabiei.