The unique properties of fluorinated organic compounds have received intense interest and have conquered a myriad of applications in the chemical and pharmaceutical sciences. Today, an impressive range of alkyl fluorides are commercially available, and there are many practical methods to make them exist. However, the unmatched stability and inertness of the C-F bond have largely limited its synthetic value, which is very different from the widely accepted utility of alkyl chlorides, bromides, and iodides that serve everyday as "workhorse" building blocks in countless carbon-carbon bond forming reactions. This study demonstrates practical and high-yielding functionalization of the C-F bond under mild conditions, i.e., at temperatures as low as -78 °C, in short reaction times and with unconventional chemoselectivity. Cryogenic Csp