The synthesis of monofluorinated compounds is of great interest because of the vast applications of organofluorine compounds. Recently, the introduction of monofluorocarbene synthons has emerged as an important strategy for the synthesis of fluorine-containing products. In contrast to direct fluorination, in which C−F bonds are formed, the use of monofluorinated carbenes and related reactive species involves C−C or C−X bond formation while delivering valuable fluorine atoms into the target structure. Owing to increased knowledge on carbon-carbon and carbon-heteroatom bond formations, monofluorinated carbenes have enormous potential for the synthesis of organofluorine compounds, which, in our opinion, has not yet been fully exploited. This review summarizes the recent advances in the synthetic applications of monofluorinated carbenes, carbenoids, ylides, and related species.