The sulfur-linked pentathiohexasaccharide 3(I),3(IV)-di-β-D- glucopyranosylthiogentiotetraose (12) has been prepared by a convergent approach involving the reaction of 1,2,4-tri-O-acetyl-6-deoxy-6-iodo-3-S- (2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)-3-thio-β-D-glucopyranose (10) with the sodium salt of 2,3,4-tri-O-acetyl-6-S-[2,4-di-O-acetyl-3,6-di- S(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)-3,6-dithio-β-D- glucopyranosyl]-1,6-dithio-β-D-glucopyranose (4). A further reaction, involving the sodium salt of the peracetylated β1-thio derivative of 12 with 1,2,3,4-tetra-O-acetyl-6-deoxy-6-iodo-β-D-glucopyranose (26), afforded the homologous sulfur-linked hexathioheptasaccharide 3(II),3(V)-di-β-D- glucopyranosylthiogentiopentaose (28). Related sulfur-linked positional isomers 3(II),3(IV)-di-D-β-glucopyranosylthiogentiotetraose (34) and 3(III),3(V)-di-β-D-glucopyranosylthiogentiopentaose (39) have been prepared using analogous synthetic strategies. Thus, S(N)2 displacement of the iodine atom in 10 by the sodium salt of 2,4-di-O-acetyl-3,6-di-S-(2,3,4,6-tetra-O- acetyl-β-D-glucopyranosyl)-1,3,6-trithio-β-D-glucopyranose afforded a tetrathiopentasaccharide, which resulted in the pentathiohexasaccharide 34 by a sequence of reactions involving the 1-thioglycose 32 in reaction with 26. The hexathioheptasaccharide 39 was obtained conveniently by the reaction of 26 with the acetylated 1-thio-6(I), 3(II), 6(II), 3(IV), 6(IV)-pentathio derivative 37, followed by deacylation. The four isomeric pentathiohexa- and hexathioheptasaccharides 12,34 and 28,39, respectively, were all found to be active in eliciting phytoalexin accumulation in soybean cotyledon tissue and in binding to a glucan-binding protein of soybean, although to a lesser extent than the corresponding O-oligosaccharides, the alternate thiohexa- and thioheptasaccharides 12,28 being more active as compared to the geminally branched isomers 34,39.