A new three-dimensional porous metal-organic framework, {[NH2(CH3)2][Zn(atz)(ox)]•H2O}n (1) (Hatz = 5-amino-1H-tetrazole, H2ox = oxalic acid), has been solvothermally synthesized and characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction analysis. Complex 1 exhibits an anionic framework that can be simplified as a rarely reported 4-connected lon network. Complex 1 could be utilized as a platform for emission tuning by doping different lanthanide ions. In addition, gas adsorption studies reveal that 1 has a high isosteric heat of CO2 and good adsorption selectivity for CO2 over CH4 and N2.