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Two protic pyrazolium ionic liquids (ILs) are synthesized and characterized by mass spectra (MS),1H NMR,13C NMR,and single-crystal X-ray diffraction.Then,their catalytic activity for the cycloaddition of PO and CO2 is investigated.Two protic pyrazolium ILs are the orthorhombic and triclinic systems of space groups Cmca and C2/c for HTMPzBr and HDMPzBr,respectively.They could catalyze the cycloaddition reaction of carbon dioxide (CO2) with epoxides (PO) to produce cyclic carbonate (PC) without any solvent and co-catalyst and show strong catalytic activity when the reaction temperature is over 110 ℃.