Chemical synthesis of the branched pentasaccharide 6'-alpha-maltosyl-maltotriose (15) is reported, based on the use of one synthon as a glycosyl acceptor and another synthon as a glycosyl donor. The synthon used as glycosyl acceptor was phenyl 2,3,6-tri-O-benzyl-1-thio-beta-D-glucopyranoside (7) and was synthesized from D-glucose with phenyl 2,3-di-O-acetyl-4,6-O-benzylidene-1-thio-beta-D-glucopyranoside and phenyl 2,3-di-O-benzyl-4,6-O-benzylidene-1-thio-beta-D-glucopyranoside as key intermediates. The synthon used as glycosyl donor was O-(2,3,4,6-tetra-O-benzyl-alpha-D-glucopyranosyl)-(1-->4)-O-(2,3,6-tri-O -benzyl - alpha-D-glucopyranosyl)-(1-->6)-O-[(2,3,4,6-tetra-O-benzyl-alpha-D- glucopyranosyl)-(1-->4)]-2,3-di-O-benzyl-alpha,beta-D-glucopyranosyl trichloroacetimidate (12) and was synthesized from phenyl O-2,3,4,6-tetra-O-benzyl-alpha-D-glucopyranosyl)-(1-->4)-O-(2,3,6-tri-O- benzyl- alpha-D-glucopyranosyl)-(1-->6)-O-[(2,3,4,6-tetra-O-acetyl-alpha-D- glucopyranosyl)-(1-->4)]-2,3-di-O-acetyl-1-thio-beta-D-glucopyranoside with O-(2,3,4,6-tetra-O-benzyl-alpha-D-glucopyranosyl)-(1-->4)-O-(2,3,6-tri-O - benzyl-alpha-D-glucopyranosyl)-(1-->4)]-2,3-di-O-benzyl-D-glucopyranose as an intermediate. Condensation of compounds 7 and 12 followed by removal of the phenylthio group and debenzylation provided the branched pentasaccharide 15. Alternatively, the branched pentasaccharide was produced from amylopectin by consecutive alpha- and beta-amylase treatments and purified by chromatography. The identity of the products obtained by chemical synthesis and enzymatic hydrolysis is documented by 1H and 13C NMR spectra.