AbstractGiven the capture and utilization of carbon dioxide (CO2) emission, the CO2 separation and catalysis fixation of CO2 and epoxides have been of intense interest. In this respect, a microporous copper‐based metal‐organic framework (MOF) Cu2(ABTC) (ABTC=3,3’,5,5’‐azobenzenetetra‐carboxylic acid) was synthesized. The Cu–MOF endowed with open Cu sites, accessible pore cages and hexagonal channel (9.6 & 11 Å) exhibits permanent porosity (BET surface area of 2200 m2 g−1), good low‐pressure CO2 uptake (93 cm3 g−1, at 298 K), and moderate CO2 selectivity over N2 and CH4. In light of catalysis fixation of CO2 and epoxides, Cu2(ABTC) exhibited outstanding performance with high conversion of styrene oxide (96 %), and yield towards the formation of styrene carbonate (90 %) under mild conditions (1 atm of CO2, 60 °C, 8 h). Notably, the catalytic activity of Cu2(ABTC) outperformed that of other Cu‐MOFs, and the recovered Cu2(ABTC) can be reused up to six times without considerable reduction in catalytic activity.