The new bifunctional ligand 4,4'-(adamantane-1,3-diyl)bis(1,2,4-triazole) (tr(2)ad) and benzene-1,3,5-tricarboxylate sustain complementary coordination bridging for the three-dimensional framework of poly[[bis[mu(3)-4,4'-(adamantane-1,3-diyl)bis(1,2,4-triazole)-kappa(3)N(1):N(2):N(1')]bis(mu(4)-benzene-1,3,5-tricarboxylato-kappa(4)O(1):O(1'):O(3):O(5))di-mu(3)-hydroxido-kappa(6)O:O:O-tetracopper(II)] dihydrate], {[Cu(4)(C(9)H(3)O(6))(2)(OH)(2)(C(14)H(18)N(6))(2)].2H(2)O}(n). The net node is a centrosymmetric (mu(3)-OH)(2)Cu(4) cluster [Cu-O = 1.9525 (14)-2.0770 (15) A and Cu...Cu = 3.0536 (5) A] involving two independent copper ions in tetragonal pyramidal CuO(4)N and trigonal bipyramidal CuO(3)N(2) environments. One carboxylate group of the anion is bridging and the other two are monodentate, leading to the connection of three hydroxide clusters and the generation of neutral coordination layers separated by 9.3583 (5) A. The interlayer linkage is effected by mu(3)-tr(2)ad ligands, with one triazole group N(1):N(2)-bridging and the second monodentate [Cu-N = 1.9893 (19), 2.010 (2) and 2.411 (2) A]. In total, the hydroxide clusters are linked to six close neighbors within the carboxylate layer and to four neighbors via tr(2)ad bridges. Hydrogen bonding of solvent water molecules to noncoordinated triazole N atoms and carboxylate groups provides two additional links for the net, which adopts a 12-connected topology corresponding to hexagonal closest packing. The study also introduces a new type of bis(triazole) ligand, which may find wider applications for supramolecular synthesis.