The reaction of commercially available 3-amino-1,2,4-triazole (Hatz) and Zn(OH)(2) at room temperature produced a porous zeolite-like metal azolate framework, [Zn(atz)(2)] (MAF-66). Single-crystal X-ray diffraction studies of MAF-66 showed that atz(-) served as an imidazolate-type ligand, linking tetrahedral Zn-II ions to form a noninterpenetrated dia framework, which contains a narrow, three-dimensional intersecting channel system (void = 49.8%) functionalized by amino groups and uncoordinated triazolate N atoms on the pore surface. Gas-sorption measurements of MAF-66 revealed high CO2 uptakes (27.6/19.4 wt % at 273/298 K and 1 atm) and high Henry's law CO2/N-2 selectivity (403/225 at 273/298 K). The host-guest interactions between CO2 and the pore surface were also studied by in situ IR absorption spectroscopy and powder X-ray diffraction measurements.