Ag/Mesoporous CeO2 (Ag/M−CeO2) catalysts were synthesized through the gas bubbling‐assisted membrane reduction (GBMR) method and characterized by XRD, ICP‐OES, N2 adsorption‐desorption, XPS, Raman spectroscopy, TEM, HRTEM, HAADF‐STEM and CO2‐TPD. Ag/M−CeO2 catalysts contain uniform mesoporous structure, large surface area and oxygen vacancies, which promote the dispersion of Ag nanoparticles. Density functional theory (DFT) calculations indicate that Ag nanoparticles supported on M−CeO2 could facilitate the formation of oxygen vacancies, which result in higher CO2 adsorption capacity. With the most oxygen vacancies and the well‐dispersed Ag active species, Ag (3.12 %)/M−CeO2 exhibits high efficiency for the carboxylative coupling of terminal alkynes, chloride compounds and CO2 under mild reaction conditions (60 °C, 0.5 MPa), affording a wide range of functionalized 2‐alkynoates in good yields.