A water-soluble polysaccharide isolated from the hot water extract of the green fruits of Capsicum annuum was found to consist of 3-O-acyl-L-rhamnose, D-methyl galacturonate, 6-O-methyl-D-galactose in a molar proportion of nearly 1:2:1. Structural investigation of the polysaccharide was carried out using total hydrolysis, methylation analysis, periodate oxidation followed by GLC-MS, and NMR experiments. On the basis of the above-mentioned experiments it is concluded that the following repeating unit is present in the polysaccharide [GRAPHICS] (C) 2009 Published by Elsevier Ltd.