A new generation-2 light-responsive metal–organic framework (MOF) has been successfully synthesized using Zn as the metal source and both 2-phenyldiazenyl terephthalic acid and 1,4-diazabicyclo[2.2.2]octane (DABCO) as the ligands. It was found that Zn-azo-dabco MOF (Azo-DMOF-1) exhibited a photoresponsive CO2 adsorption both in static and dynamic condition because of the presence of azobenzene functionalities from the ligand. Further application of this MOF was evaluated by incorporating it as a filler in a mixed matrix membrane for CO2/N2 gas separation. Matrimid and polymer of intrinsic microporosity-1 (PIM-1) were used as the polymer matrix. It was found that Azo-DMOF-1 could enhance both the CO2 permeability and selectivity of the pristine polymer. In particular, the Azo-DMOF-1–PIM-1 composite membranes have shown a promising performance that surpassed the 2008 Robeson Upper Bound.