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A series of carbon sphere supported with adjustable alkyl length substitutes polymeric ionic liquids bearing hydroxylamino-anchored functional groups by covalent connection were fabricated from copolymerization of carbon sphere with vinyl based monomeric ionic liquids, which were constructed from 1-glycidyl-3-vinylimidazolium bromide and alkyl amines. The carbon sphere hybrid polymeric ionic liquids were characterized by FT-IR, SEM–EDS, N2 adsorption/desorption isotherm, elemental analysis, 13C MAS NMR and XPS, which were candidated as heterogeneous catalysts for CO2-epoxide cycloaddition reactions to product cyclic carbonates at mild conditions without co-catalyst and metal ion. The introduced functional groups on carbon sphere could accelerate the reaction process and yields of above 90% were obtained for various cyclic carbonates under optimized conditions. Finally, kinetic experiments were also carried out to reveal reaction mechanism and the activated energy was determined as 114.9 kJ/mol. Therefore, this study provides a new approach to fabricate multifunctional heterogeneous materials for coupling reaction of CO2 under mild conditions. [ABSTRACT FROM AUTHOR]