A review of metal-catalysed carbonylation reactions involving single-electron transfer mechanisms and organic radical intermediates is presented, emphasizing new avenues to carbonyl compounds that are enabled by this approach. Catalyst-induced, oxidant-induced, and photo-induced radical carbonylations are discussed, as are atom-transfer carbonylation chain processes. Collectively, this body of carbonylative coupling chemistry complements more traditional precious metal-based catalytic systems that engage in substrate carbonylation by two-electron pathways.