Carboxylation of terminal alkynes with CO2 via direct C–H bond activation is a highly appealing way to capture and convert CO2 but faces great challenges and difficulty. Here, we report an efficient catalyst that is prepared simply through introduction of p-tert-butylaniline into graphite oxide powders followed by localized growth of Ag nanoparticles (NPs). The bulky nature of p-tert-butylaniline facilitates the powder exfoliation, giving rise to mass production of uniform modified graphene oxide (tert-GO) nanosheets of 4 nm in thickness. Notably, Ag/tert-GO shows excellent catalytic activity for converting alkynes regardless of containing electron-donating or electron-withdrawing groups under mild reaction conditions. The synergy of the amide linkages on tert-GO nanosheets and the supported small-sized Ag NPs is recognized as the vital role in promoting adsorption of CO2 and subsequent conversion.