The first chemo- and site-selective process for the formation of N-aryl-carbamates from cyclic organic carbonates and aromatic amines is reported. The reactions proceed smoothly under extremely mild/attractive reaction conditions using TBD (triazabicyclodecene) as an effective and cheap organocatalyst providing a sustainable and new methodology for the formation of a wide variety of useful N-aryl carbamate synthons in good to excellent yields. Computational investigations have been performed showing the underlying reason for the observed unique reactivity which is related to an effective proton-relay mechanism mediated by the bicyclic guanidine base.