Cobalt-catalyzed carboxyzincation reactions employing carbon dioxide and zinc metal powder are developed. By using alkynes as substrates, regio- and stereodefined (Z)-beta-zincated acrylates are provided. The corresponding alkenylzinc moiety can be converted to various substituents, affording multisubstituted acrylic acids. Furthermore, by adding electron-deficient alkene to the reaction system, the four-component coupling reactions of alkyne, alkene, CO2, and the Zn atom proceed via carboxyzincation.