Gold nanoparticles function as single-electron transfer catalysts to promote decarboxylative cross-coupling between N-hydroxy phthalimide (NHPI) esters and disilanes or diborons. A variety of disilanes coupled with alkyl radicals could be gen-erated from NHPI esters via single-electron reduction by active carbon-supported gold nanoparticle catalysts to afford di-verse alkylsilanes without the need for external bases. Furthermore, the present Au catalytic system was also effective for decarboxylative C–B coupling to afford alkyl boronates. A detailed mechanistic investigation revealed that single-electron transfer mediated by supported gold nanoparticles enabled the generation of alkyl radical and silyl radical, thereby enabling radical cross-coupling. The reusability and environmentally-friendly nature of supported gold catalyst as well as the scalabil-ity of the reaction system enable the practical transformation of carboxylic acid derivatives into value-added organosilicon and organoboron compounds.