A metal phosphonate coordination polymers, [Zn2(tdp)(tpt)·H2O]n (named as IMNU-1, wherein tdp = thiophene-2,5-diphosphonic acid, tpt = 2,4,6-tritri(pyridin-4-yl)-1,3,5-triazin) has been successfully synthesized under hydrothermal conditions. Built from nitrogen-rich azole and {Zn4O12} cluster, IMUN-1 possesses abundant of Lewis acid/alkali sites and shows effective catalytic activity in the CO2 chemical fixation and in the ring-opening reaction. The TOF values are higher than most reports on MOFs-based catalysts. Additionally, its activity wasn’t compromised after five recycles with a total TON value of 31,605. The feasible mechanism of catalytic reaction was proposed. Furthermore, IMUN-1 exhibits extremely thermal and chemical stability, especially the resistance to hydrolysis, acid and alkali. The exceptional catalytic activity and remarkable stability render it potential for practically industrial applications.