As an important and attractive C1 building block, the diversified exploitation of CO2in chemical transformations possesses significant research and application value. Herein, an effective palladium-catalyzed intermolecular hydroesterification of a wide range of alkenes with CO2and PMHS is described, successfully generating diverse esters with up to 98% yield and up to 100% linear-selectivity. In addition, the palladium-catalyzed intramolecular hydroesterification of alkenylphenols with CO2and PMHS is also developed to construct a variety of 3-substituted-benzofuran-2(3H)-ones with up to 89% yield under mild conditions. In both systems, CO2functions as an ideal CO source with the assistance of PMHS, thus smoothly participating in a series of alkoxycarbonylation processes.