Abstract One‐pot tandem synthesis of cyclic carbonates from olefins and CO 2 is becoming one of the most potential strategies to fix CO 2 and yield high value chemicals. However, this reaction route is in need of high performing catalysts with multifunctionalized catalytic sites in single material which is still a big challenge in one‐pot community. In this term, we combined dimension reduction and surface modification strategies to fabricate a MOF/metal complex composite, that is, Zr‐BTB/PA‐Co. In this composite, the increased Lewis base sites is capable of boosting the adsorption and activation of CO 2 , which further acted as nucleophilic groups to activate epoxides, while the 2D matrix offered accessible intrinsic Lewis acid sites. These advantages synergistically led to superior catalytic performance of Zr‐BTB/PA‐Co for catalyzing one‐pot reaction of olefins and CO 2 under mild conditions (80°C, 1 bar, 12 h and co‐catalyst/solvent free), and even impressive catalytic activity when using CO 2 directly from air.