Crystals of the tetrasaccharide, (2,3,4,6-tetra-O-acetyl-beta-D-glucopyranosyl)-(1-->3)- [2,3,4,6-tetra-O-acetyl-beta-D-glucopyranosyl-(1-->6)]- (2,4-di-O-acetyl-beta-D-glucopyranosyl)-(1-->3)- 1,2,4,6-tetra-O-acetyl-beta-D-glucopyranose, belong to the monoclinic system, space group P2(1), with a = 12.709(4), b = 27.767(9), c = 9.567(4) A, beta = 105.07(2) degrees, and Z = 2. The crystal structure was solved by the direct method and refined by the full-matrix least-squares procedure to an R-value of 0.071 for 302- observed reflections in the X-ray data. All the four D-glucopyranose residues have the usual 4C1 chair conformations. The torsional angles at two (1-->3)-beta-linkages were phi(O-5-1-O-1-C-3) = -74 degrees and psi (C-1-O-1-C-3-C-2) = -122 degrees between the nonreducing and the middle residues, and phi = -67 degrees, psi = -111 degrees between the middle and the reducing residues. The orientation about the (1-->6)-beta-linkage was found to be phi(O5-C1-O-1-C-6) = -77 degrees, theta(C1-O-1-C-6-C-5) = 160 degrees, and chi(O-1-C-6-C-5-O-5) = 63 degrees (gt conformation). The primary acetate groups at C-6 of the reducing and the (1-->6)-branched residues were in the gt conformations (O-5-C-5-C-6-O-6 = 81 degrees and 84 degrees, respectively). On the other hand, the gg conformation was observed for the primary acetate group in the nonreducing residue (O-5-C-5-C-6-O-6 = 78 degrees).