Monofluoroalkanes are important in many pharmaceuticals, agrochemicals and functional materials. However, the lack of easily available and transformable monofluoroalkylating reagents that facilitate a broad array of transformations has hampered the application of monofluoroalkylation. Herein, we report a general and efficient method of preparing diverse aliphatic monofluorides with monofluoroalkyl triflate as the synthetic scaffold. Using both nickel‐catalyzed hydromonofluoroalkylation of unactivated alkenes and copper‐catalyzed C−C bond formation, the general diversification of the monofluoroalkylating scaffold has been exhibited. The broad utility of this monofluoroalkylating reagent is shown by concise conversion into various conventional fluoroalkylating reagents and construction of monofluoro‐alkoxy, ‐alkylamino motifs with commercially available heteroatom‐based coupling partners. A general method allows preparation of diverse monofluorides based on the monofluoroalkyl triflate scaffold. Both nickel‐catalyzed hydromonofluoroalkylation of unactivated alkenes and copper‐catalyzed monofluoroalkylation of Grignard reagents were studied. Further utilities including conversion into conventional fluoroalkylating reagents and construction of monofluoro‐alkoxy, ‐alkylamino motifs.