Abstract Condensation of 1′,2,2″,3,3′,3″,4,4′,4″,6′-deca-O-acetylraffinose (1) with 2,3,4,6-tetra-O-benzyl-d-galactopyranosyl chloride in the presence of tetraethylammonium chloride, followed by deacetylation, debenzylation and subsequent acetylation afforded stachyose tetradecaacetate. An isomer in which a terminal d-galctopyranosyl group is attached to the 6″-O of raffinose in β-anomeric linkage, was prepared by condensing 1 with 2,3,4,6-tetra-O-acetyl-α-d-galactopyranosyl bromide in the presence of mercury(II) cyanide. 13C NMR spectra of stachyose tetradecaacetate and the isomer were discussed.