Fluorochemicals have a wide range of applications in industry, but accessing these relies on the energy intensive conversion of acid-grade fluorspar (CaF2) to toxic hydrogen fluoride (HF) gas, which is in turn used for the downstream production of fluorochemicals via multistep processes. Now, directly treating acid-grade fluorspar with dipotassium hydrogen phosphate (K2HPO4) under mechanochemical conditions affords a fluorinating reagent for direct S–F and C(sp3/sp2)–F bond construction, bypassing the need for HF production.