The radical carbonylation, irrespective of whether the starting radicals being the alkyl, alkenyl, or aryl radicals, produces acyl radicals as the first intermediates, which are transformed to a variety of carbonyl compounds, such as aldehydes, ketones, esters, amides, and some other compounds via carbonylation. This chapter overviews the recent advances in radical carbonylation together with quick overview of previous achievements. The atom-transfer carbonylation (ATC), which does not require radical mediators, has now stimulated the developments of many useful transition-metal/radical hybrid systems, in which the key carbonylation step is radical carbonylation rather than migratory CO insertion to metal–alkyl bonds. New trends of radical carbonylation based on one-electron transfer system is also discussed in this chapter, which is well featured as electron transfer carbonylation (ETC).