Recently, efficient chemical conversion of CO2 into high value chemicals at room temperature and atmospheric pressure without using noble metal catalysts remains a great challenge. In this work, we find that the carboxylative cyclization of propargylic alcohols with CO2 can proceed at 60 degrees C and ambient pressure by using a combination of CuI and an ionic liquid (IL) 1,8-diazabicyclo-[5.4.0]-7-undecenium trifluoroethanol ([DBUH] [TFE]) as catalyst. By simple extraction after the reactions, a series of desired products have been obtained in good to excellent yields with this highly efficient catalyst system. Spectroscopic investigations and DFT calculations demonstrate that such a high efficiency originates from remarkable synergistic catalysis between Cu(I) and the IL on substrates. In addition, it is worth noting that this catalyst system also works well for the carboxylative cyclization of propargylic amines even at ambient temperature and pressure, with the highest turnover number among the reported base metals catalytic systems.