AbstractCalcium fluoride is the ultimate source of all fluorochemicals. Current synthetic approaches rely on the use of HF, generated from naturally occurring fluorspar and sulfuric acid. Methods for constructing E–F bonds directly from CaF₂ have long been frustrated by its high lattice energy, low solubility and impaired fluoride ion nucleophilicity. Little fundamental understanding of the reactivity of Ca–F moieties is available to guide methodology development; well-defined molecular species containing Ca–F bonds are extremely rare, and existing examples are strongly aggregated and evidence no nucleophilic fluoride delivery. Here, by contrast, we show that by targeting anionic systems of the type [L_n(X)₂CaF]⁻, monomeric calcium fluoride complexes containing single Ca–F bonds can be synthesized, including via routes involving fluoride abstraction from existing C–F bonds. Comparative structural and spectroscopic studies of mono- and dinuclear systems allow us to define structure–activity relationships for E–F bond formation from molecular calcium fluorides.