The basement membranes of the innervated surface of the electric organ of Discopyge tschudii present a high concentration of mucopolysaccharides as revealed by intense ruthenium red-positive reaction. Glycosaminoglycans (GAGs) were isolated and characterized from these pure basement membranes by using a combination of agarose gel electrophoresis and enzymatic degradation with specific enzymes. The isolated basement membrane showed a high concentration of GAGs (130 mg/g of dry tissue); of this amount 49% was hyaluronic acid, 24% was chondroitin-6-sulfate, 12% was heparan sulfate, and 14% was dermatan sulfate. Controlled digestion with heparinase and heparitinases I and II was used to study the structural features of the heparan sulfate. Four unsaturated disaccharide units were found in the heparan sulfate: disulfated, N-sulfated, N-acetylated, and N-acetylated O-sulfated disaccharides. The disaccharide units of the cholinergic heparan sulfate present a high amount of disulfated disaccharides and a low amount of N-acetylated O-sulfated disaccharides. The N-sulfated disaccharides, in contrast to the N-acetylated ones, were found through all the structure of the cholinergic heparan sulfate. Finally our work shows for the first time the presence of dermatan sulfate in the basal lamina of the electric organ.