Two new three-dimensional supermolecules having closed hollow frameworks were isolated by self-assembly of a tris(Zn2+-cyclen) (Zn3L3) (L-3 = 1,3,5-tris(1,4,7,10-tetraazacyclododecan-1-ylmethyl)benzene) with di- (CA(2-)) or trideprotonated cyanuric acid (CA(3-)) in aqueous solution (cyclen = 1,4,7,10-tetraazacyclododecane). One was a very stable 2:3 complex of Zn3L3 and CA(2-) formed above pH 6, which was isolated from a 2:3 mixture of Zn3L3 and cyanuric acid (CA) in aqueous solution and characterized by H-1 NMR and potentiometric pH titration. The X-ray crystal structure showed that each CA(2-) is sandwiched between two Zn2+-cyclen moieties extended from two tris(Zn2+-cyclen). The crystal data: formula C75H147N36O36Cl3Zn6 ((Zn3L3)(2)-(CA(2))(3). 3NO(3). 3ClO(4). 6H(2)O), M-r = 2627.84, monoclinic, space group P2(1)/n (No. 14), a = 27.327(3) Angstrom, b = 29.127(2) Angstrom, c = 16.025(2) Angstrom, beta = 90.56(1)degrees, V = 12754(1) Angstrom(3), Z = 4, R = 0.091, and R-w = 0.110. The second one was an unexpected supramolecular complex by 4:4 self-assembly of Zn3L3 and CA(3-), which was isolated by allowing a 1:1 mixture of Zn3L3 and CA in aqueous solution to stand at pH 11.5. Its X-ray crystal analysis showed a highly symmetric 4:4 assembling complex having an inner hollow, which was schematically represented as a truncated tetrahedron made by binding four equilateral triangles and four scalene hexagons to each other through CA(3-)-Zn2+ bends. Crystal data of the 4:4 supramolecular complex: formula C144H344N72O88Zn12 ((Zn3L3)(4)-(CA(3-))(4). 12NO(3). 40H(2)O), M-r = 5277.29, cubic, space group I (4) over bar 3m (No. 217), a = 23.430(4) Angstrom, V = 12862(3) Angstrom(3), Z = 2, R = 0.068, and R-w = 0.086. The 2:3 supercomplex is stable in H2O, while the 4:4 complex is stable only in solid or in DMSO solution and tends to go back to the 2:3 complex in the presence of H2O. The 2:3 and 4:4 complexes were equivalent in terms of acid-base equilibrium, and direction of the disproportionation to the 4:3 complex was favored due to its insolubility.