In recent years increasing attention has been given to the efficacious synthesis of organic carbonates from sustainable CO2. The carboxylation/hydration reaction of alcohols with CO2 stands out for its environmentally friendly and economic features. However, it faces several substantial challenges such as thermodynamic limitations, low catalytic efficiency, and product selectivity. In this article, recent advances in the development of catalytic methods for the synthesis of organic carbonates through carboxylation/hydration reaction of alcohols with CO2 are summarized. Catalytic schemes (metal and metal‐free catalysis), water‐dehydration strategies, and catalytic mechanisms are also discussed in detail. The review covers the carbonylation cyclization of various alcohols and the equivalent of CO2, i.e. urea. Finally, an overview is provided of the recent breakthrough in the development of thermodynamically favorable processes involving alcohols and CO2. © 2018 Society of Chemical Industry and John Wiley & Sons, Ltd.