A series of N‐heterocyclic carbene (NHC)/Ag systems were developed for the carboxylative assembly of propargylic alcohols and carbon dioxide (CO 2). With the catalysis of these catalytic systems, a variety of target α‐alkylidene cyclic carbonates could be obtained smoothly under atmospheric CO 2 pressure in straightforward one‐pot processes. Particularly, these reactions could be performed without any stoichiometric addition of bases or additives. Further mechanistic investigation reveals that the excellent activities are attributed to the effective activations of CO 2 accomplished by the NHCs via the formation of the NHC‐CO 2 adducts.