Ba(ClO4)2.3H2O, Mr = 390.28, hexagonal, P63/m, a = 7.277 (2), c = 9.656 (1) A, V = 442.9 (1) A3, Z = 2, F(000) = 368, D chi = 2.93 g cm3, lambda(Mo K alpha) = 0.71069 A, T = 295 K, mu = 52.60 cm1, 456 unique reflections, R = 0.023. The barium atoms in this structure are coordinated by six water oxygens, O(3), at 2.919 (1) A and by six perchlorate oxygens, O(2), at 3.026 (2) A in a slightly distorted icosahedral arrangement, the average Ba-O separation thus being approximately 2.97 A. The perchlorate ion just fails to have regular tetrahedral geometry within the experimental error, and has an average Cl-O bond length of 1.433 (6) A. Consistent with hydrogen bonding delineated on the basis of least-squares-refined hydrogen-atom positions, each axial [O(1)] perchlorate oxygen is hydrogen bonded to three water molecules and each trigonal [O(2)] perchlorate oxygen is hydrogen bonded to two water molecules; thus each perchlorate ion is hydrogen bonded to nine water molecules. Conversely, each water molecule [O(3)] oxygen is hydrogen bonded to six perchlorate ions to two through axial [O(1)] oxygens and to four through trigonal [O(2)] oxygens.