The non-lichenized ascomycete Bulgaria inquinans (Fries), growing in the Changbai Mountain of China, has been used as medicinal diet for many years. In a previous study, we have reported that a heteropolysaccharide BIWS-4b from the fruit bodies of B. inquinans (Fries) exhibited markedly antimalarial and immunostimulating activities. In this paper, the structural features and antioxidant activity of BIWS-4b were investigated. The results showed that BIWS-4b contains an alpha-(1 -> 2), (1 -> 6)-mannan core to which the glucogalactan chains are attached. The glucogalactan chains were composed of (1 -> 6)-, (1 -> 5)- and (1 -> 5,6)-linked beta-Galf, (1 -> 4)-linked and non-reducing terminal beta-Glcp units, and might be attached to the mannan core at the O-2 positions of alpha-Manp units. The antioxidant assays showed that BIWS-4b exhibited good activities, including free radicals scavenging effects, ferrous ion-chelating ability and reducing power. Thus, BIWS-4b could be used as a natural antioxidant agent for food and pharmaceutical industries. (c) 2012 Elsevier Ltd. All rights reserved.