Acid-catalyzed thiophenolysis of per-O-acetylated 1,6-anhydromaltose (3) gave phenyl 2,3-di-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-alpha-D- glucopyranosyl)-1-thio-beta-D-glucopyranoside (4) in quantitative yield. Phenyl 4-O-alpha-D-glucopyranosyl-1-thio-beta-D-glucopyranoside (5) was obtained by acid-catalyzed thiophenolysis of maltose octaacetate (2), using trimethylsilyl triflate as catalyst, and subsequent deacetylation. Standard benzylation of 5 gave phenyl 2,3-di-O-benzyl-4-O- (2,3,4,6-tetra-O-benzyl-alpha-D-glucopyranosyl)-1-thio-beta-D-glucopy ran oside (6) which upon treatment with N-bromosuccinimide in aqueous acetone gave 2,3,6-tri-O-benzyl-4-O-(2,3,4,6-tetra-O-benzyl-alpha-D- glucopyranosyl)-D-glucopyranose (8). Compound 8 was treated with trichloroacetonitrile in the presence of anhydrous potassium carbonate to give 2,3,6-tri-O-benzyl-4-O-(2,3,4,6-tetra-O-benzyl- alpha-D-glucopyranosyl) -alpha,beta-D-glucopyranosyl trichloroacetimidate (9), which was effectively used as the glycosyl donor in the condensation reaction with compound 4, using trimethylsilyl triflate as catalyst, to obtain the branched tetrasaccharides 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-be ta-D- glucopyranoside (10) and phenyl O-[(2,3,4,6-tetra-O-benzyl-alpha-D-glucopyranosyl)-(1-->4)]- O-(2,3,4-tri-O-benzyl-beta-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-glucopy ran oside (11) in 67 and 21% yield, respectively. A complete NMR interpretation of 10 is presented. Alternative methodologies for the synthesis of the branched tetrasaccharides were investigated. Chemical synthesis of the phenyl thioglycoside 5 was achieved by deacetylation of 4. Reaction of 6 with diethylaminosulfur trifluoride in the presence of N-bromosuccinimide gave 2,3,6-tri-O-benzyl-4-O-(2,3,4,6-tetra-O-benzyl-alpha-D- glucopyranosyl)-alpha,beta-D-glucopyranosyl fluoride (7) in 78% yield. Subsequent condensation of 7 and 4, using the combination silver perchlorate-stannous chloride as catalyst, gave the corresponding branched tetrasaccharides 10 and 11 in 55 and 10% yield, respectively.