Synthetic methods for the preparation of per- O-acetylated, (1→6)-linked disaccharides containing either a d-galactose or a d-glucose residue at the reducing end are described. In these methods, 1,2,3,4-tetra- O-acetyl-6- O-trityl-β- d-glucopyranose was first converted into 1,2,3,4-tetra- O-acetyl-β- d-glucopyranose ( 1) by rapid treatment with 90% trifluoroacetic acid, followed by rapid isolation designed to minimize O-acyl migration. Disaccharides were formed by glycosylation of 1 or 1,2:3,4-di- O-isopropylidene- d-galactopyranose with per- O-acetylglycosyl halides. Isopropylidene groups in the resulting disaccharide, if present, were removed, and the disaccharide was per- O-acetylated. Per- O-acetylated β-Gal-(1→6)-Glc and β-GlcNAc-(1→6)-Gal, and a mixture of per- O-acetylated α-Gal-(1→6)-Gal and β-Gal-(1→6)-Gal (in the ratio of 3:7) were thus obtained. The per- O-acetylated Gal-(1→6)-Gal disaccharides were converted, by a reaction sequence previously reported, into (2,2-dimethoxyethyl)aminocarbonylmethyl 1-thio-β- d-glycosides, which could then be coupled to proteins via reductive alkylation. For the anomeric mixture of per- O-acetylated Gal-(1→6)-Gal, conversion into the corresponding 1-thioglycoside permitted resolution of the isomers by chromatography on silica gel. When disaccharides, as borate complexes, were chromatographed on a column of a strong, anion-exchange resin, all of the (1→6)-linked disaccharides of neutral sugars tested (including melibiose) were eluted later than analogous disaccharides having other linkages, and also later than any neutral monosaccharides.