The non-toxic biologic material carboxymethyl cellulose (CMC) supported imidazolium-based ionic liquids (ILs), coupling with a series of Lewis acids has been prepared and used as heterogeneous catalysts for the cycloaddition of CO2 to cyclic carbonate. The as-synthesized catalysts have been characterized by FT-IR, XRD, TGA, SEM etc. Especially, the protonated CMC (HCMC) supporting both the hydroxyl group functionalized IL (1-hydroxypropyl-3-n-butylimidazolium chloride, HBimCl) and NbCl5 (HBimCl-NbCl5/HCMC) exhibited the best catalytic performance. It was indicated that HBimClon HBimCl-NbCl5/HCMC catalyst was highly leaching-resistant even if it was immobilized through non-covalent interaction. The IL and Lewis acid exhibited strong synergistic effects for the cycloaddition reaction. Additionally, the HBimCl-NbCl5/HCMC catalyst exhibited a high activity and excellent selectivity for a wide scope of substrates under optimum conditions and also it was further extended to application in the continuous fixed-bed flow reactor and showed an excellent catalytic stability. No loss of catalytic activity was observed even after 120 h on stream. (C) 2016 Elsevier B.V. All rights reserved.