As an important type of crystalline porous solid material, metal−organic frameworks (MOFs) are extensively investigated with respect to gas storage/separation,catalysis,proton conduction,and drug delivery.However, in view of their similarities, C2H2/CO2 separations are only realized for a few MOFs.8 Even so, claims of C2H2/CO2 separation performance for most MOFs are solely supported by their single-component adsorption data. The breakthrough experiments based on a binary mixture,9 which provides the actual separation performance of porous materials, are absent for most MOFs.