A microporous metal–organic framework {[Cu 3 Cl 6 (ttmb) 4 ]·6H 2 O} n (1) (ttmb=1,3,5-tris(1,2,4-triazol-1-ylmethyl)-benzene) with tetranodal (3,4)-connected topological type was prepared by the self-assembly reaction of the flexible tripodal ligand ttmb with CuCl 2 ·2H 2 O. The ligand exhibits two infrequent coordination conformations in complex 1, and the framework has a large pore volume (remove the solvent molecules) of 1781.6Å 3 (36.3% of the total). The test of 1 as the catalyst in the oxidative coupling reaction of 2,6-dimethylphenol indicates that it is catalytically active by showing high conversion of DMP under the optimized reaction condition.