Computational crystal construction algorithms were used to create twelve metal-organic frameworks containing a newly synthesized [2,2′-bithiazole]-5,5′-dicarboxylic acid (H₂TzTz) spacer and assorted transition metal nodes. Among the twelve structures, the zirconium-based MOF of general formula [Zr₆O₄(OH)₄(TzTz)₆] (1) was found to be the best candidate for carbon dioxide uptake, as judged from the results of the grand canonical Monte Carlo (GCMC) simulations of CO₂ adsorption isotherms. Guided by the simulation results, 1 was synthesized in the laboratory and thoroughly characterized. 1 is isoreticular to its bithiophene and bis(benzene) (UiO-67) analogues; it crystallizes in the cubic Pn3 space group with fcu topology, and it features octahedral [Zr₆] nodes connected by twelve carboxylate groups from six bridging TzTz^2- spacers. It is a predominantly microporous material (micropore volume = 84% of the total pore volume), with a BET area of 840 m² g^-1 and a maximum CO₂ uptake at ambient pressure of 2.3 mmol g^-1 (10.0 wt%) or 1.7 mmol g^-1 (7.5 wt%) at 273 or 298 K, respectively. The CO₂ affinity (isosteric heat of adsorption Q_st = 18.7 kJ mol^-1; CO₂/N₂ Henry selectivity = 10; CO₂/N₂ IAST selectivity = 8.4) is similar to that of its bithiophene analogue. After partial removal of solvent (activation), 1 was tested as a heterogeneous catalyst in the reaction of CO₂ with epoxides bearing a-CH₂X pendant arm (X = Cl: epichlorohydrin; X = Br: epibromohydrin) to give the corresponding cyclic carbonates at T = 393 K and p_CO2 = 1 bar under green (solvent-and co-catalyst-free) conditions. A good conversion of 74% and a turnover frequency of 12.3 mmol (cyclic carbonate) per mmol_Zr per h have been recorded with epibromohydrin as a substrate.