Difunctionalization of alkenes enables construction of complex compounds in one pot. In this report, we presented an intermolecular, redox‐neutral three‐component dicarbofunctionalization of activated alkenes under mild reaction conditions. The mechanistic studies indicated tertiary alkyl radicals from oxalate salts were first added to alkenes in Giese‐type fashion, followed by nucleophilic addition with aldehydes to produce the desired 1,2‐dialkylation products. The catalyst system does not require any additives, with good functional group compatibility, regioselectivity, and constructs two tertiary carbon centers simultaneously. [ABSTRACT FROM AUTHOR]