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The utilization of CO2 from flue gas as a C1 feedstock for the catalytic synthesis of high-valued oxazolidinones is highly important but challenging due to the low CO2 concentration and high activation barrier for CO2. Herein, we present an efficient and stable CuI-anchored porous covalent organic framework CuI@TpBD-COF for effective catalysis of the carboxylic cyclization reaction between propargylic amines and CO2 to produce various functionalized oxazolidinone derivatives under mild conditions. The yield is up to 99% and the turnover frequency (TOF) reaches a record value of 1058 h−1, significantly surpassing almost all previously reported metal heterogeneous catalysts. Furthermore, CuI@TpBD-COF also demonstrates efficient catalytic activity when simulated flue gas is used as the source of CO2. This work provides new guidance for the design of more efficient and eco-friendly noble-metal-free catalytic materials to drive the ideal CO2 chemical fixation process. [ABSTRACT FROM AUTHOR]