The water-soluble polysaccharide-containing fraction from Solanum virginianum leaves upon anion exchange chromatography yielded a highly branched pectic arabinogalactan-containing fraction (F2). Herein, direct evidences for the (i) presence of a chain having 1,6-linked Gal units substituted at O-3, (ii) coexistence of Ara and Gal residues in the same molecule, (iii) existence of a chain containing 1,3-linked Gal p residues substituted at C-6, and (iv) occurrence of 1,5-linked Ara f residues substituted at O-3 were presented. This polysaccharide that showed a dose-dependent antioxidative property formed a water-soluble complex with bovine serum albumin. Thus, F2 could be used as a natural ingredient in functional food and pharmaceutical products to mollify oxidative stress.