A three-dimensional microporous metal-organic framework, Zn(5)(BTA)(6)(TDA)(2)·15DMF·8H(2)O (1; HBTA = 1,2,3-benzenetriazole; H(2)TDA = thiophene-2,5-dicarboxylic acid), comprising pentanuclear [Zn(5)] cluster units, was obtained through an one-pot solvothermal reaction of Zn(NO(3))(2), 1,2,3-benzenetriazole, and thiophene-2,5-dicarboxylate. The activated 1 displays type-I N(2) gas sorption behavior with a Langmuir surface area of 607 m(2) g(-1) and exhibits interesting selective gas adsorption for C(2)H(2)/CH(4) and CO(2)/CH(4).