ConspectusTransition-metal-catalyzed carbonylation coupling methods have been accepted as an essential tool for producing carbonylated products over the past few decades. Despite its long-standing history and widespread industrial applications, several challenges remain in carbonylation chemistry. These include reliance on precious metal catalysts, the need of high-energy radiation, difficulties in carbonylation of unactivated chemical bonds, etc. As an alternative to classic two-electron transfer process, single-electron-transfer (SET)-mediated carbonylation has emerged as a powerful tool to achieve elusive carbonylation transformations. Over the past few years, carbonylation of commonly available functional handles, such as alkenes and alkyl halides, via the single-electron pathway has emerged as a valuable area of research.Our team has been dedicated to developing new carbonylation reactions using bulk chemicals to construct high-value carbonylated products. These reactions have broad synthetic and industrial applications, motivating us to explore SET-mediated carbonylation transformations for two key classes of bulk chemicals: alkanes and alkyl halides. Specifically, our work has centered on two main approaches: (1) Single-electron reduction of C(sp