Two novel metal−organic frameworks (MOFs) Zn(TITMB)(OAc)(OH)·8.5H2O (1) and Ag(TITMB)N3·H2O (2) TITMB = 1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene, OAc = acetate anion were synthesized and their structures were determined by X-ray crystallography. Complex 1 crystallizes in tetragonal space group P4̄ with a = 23.2664(7) and c = 11.9890(3) Å and Z = 8. 1 has a one-dimensional tubelike structure with large inner pore size of ∼17 Å. Complex 2 crystallizes in monoclinic space group C2 with a = 20.7193(10), b = 11.5677(8), and c = 12.2944(6) Å, β = 125.5770(10)°, and Z = 4. 2 consists of two-dimensional honeycomb networks that interpenetrate each other to generate a polycatenated structure. In these two complexes, both zinc(II) and silver(I) atoms are four-coordinated with the same tetrahedral coordination geometry. The topologies of 1 and 2 are predominated by the conformations of TITMB, which are cis, trans, trans in 1 and cis, cis, cis in 2, respectively.