Solvothermal reaction of [1,1′-biphenyl]-3,3′,5,5′-tetracarboxylic acid (H₄bptc), 3,5-diamine-1H-1,2,4-triazole (Hdatrz) and zinc acetate affords a three-dimensional structure of [Zn₂(bptc)(datrz)](CH₃)₂NH₂·2H₂O (MAC-6). It is a (3,6)-connected framework built of paddle-wheel and triazolate-dinuclear metal clusters together with bptc ligands, and shows a novel (4².6)₂(4⁴.6⁶.8⁵) topology. Heating crystal samples of MAC-6 leads to the structure transformation to [Zn₂(bptc)(datrz)(H₂O)_0.5](CH₃)₂NH₂·H₂O (MAC-6′), in which the paddle-wheel unit deforms to a dinuclear unit. Remarkably, MAC-6′ can reversibly recover to MAC-6 when the samples of MAC-6′ were immersed into DMF. The deformation and reformation of the paddle-wheel unit were studied by single-crystal-to-single-crystal (SCSC) transformation. In addition, their photoluminescent properties were also studied.