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• Targeted design, convenient synthesis and detailed characterization of the catalyst. • Cooperative catalysis, mild conditions and general applicability for CO 2 utilization. • Prominent recyclability, simple separation and efficient gram-scale processes. Herein, a novel fiber-supported N-heterocyclic carbene (NHC) precursor and copper(I) composite (EIMBr-PANF TA @CuI), capable of acting as a cooperative catalyst for cleaner carboxylation of terminal alkynes from CO 2 , is presented. The EIMBr-PANF TA @CuI was synthesized systematically, and the resulting fiber samples from preparation and utilization processes were characterized detailedly. Moreover, the unique fiber-supported composite structure as a cooperative catalyst exhibited the synergistic effect on the activation of CO 2 and terminal alkyne, which corporately contributed to the high catalytic performance on carboxylation for producing a series of alkyl 2-alkynoates in acetonitrile under ambient conditions. Furthermore, EIMBr-PANF TA @CuI was stable to air and moisture, and could be easily recovered with a tiny pair of tweezers and recycled with good activity over 10 runs. In addition, this protocol was convenient and effective for gram-scale experiments and thereby was prospective in practical applications. [ABSTRACT FROM AUTHOR]