An expansive array of medicines, agrochemicals, and materials contain fluorine due to the unique chemical properties that the element confers on organic molecules. One of the chief obstacles to the discovery and production of these compounds is the availability of synthetic methods for carbon–fluorine (C–F) bond formation. The most abundant and inexpensive fluorine sources, nucleophilic fluoride salts, typically suffer from low solubility, high hygroscopicity, and strong Brønsted basicity, rendering them recalcitrant reagents for chemical synthesis. Nevertheless, our laboratory has recently identified two strategies that achieve mild and efficient nucleophilic fluorination using transition metal catalysis. These stereoselective methods represent exciting platforms for the invention of a wide spectrum of chemical transformations. Through mechanistic studies, we are interested in assembling a better understanding of the properties and reactivity of transition metal fluorides. Ultimately, our efforts may enable the discovery and manufacture of novel pharmaceuticals, materials, and small-molecule tracers for positron emission tomography (PET).