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The use of fluorspar to produce fluorochemicals via a process that bypasses HF is highly desirable but remains an unsolved problem because of the prohibitive insolubility of CaF\n            <jats:sub>2<\/jats:sub>\n            . Inspired by calcium phosphate biomineralization, we herein disclose a protocol of treating acid-grade fluorspar with dipotassium hydrogen phosphate (K\n            <jats:sub>2<\/jats:sub>\n            HPO\n            <jats:sub>4<\/jats:sub>\n            ) under mechanochemical conditions. The process affords a solid composed of crystalline K\n            <jats:sub>3<\/jats:sub>\n            (HPO\n            <jats:sub>4<\/jats:sub>\n            )F and K\n            <jats:sub>2\u2212<\/jats:sub>\n            <jats:italic>\n              <jats:sub>x<\/jats:sub>\n            <\/jats:italic>\n            Ca\n            <jats:italic>\n              <jats:sub>y<\/jats:sub>\n            <\/jats:italic>\n            (PO\n            <jats:sub>3<\/jats:sub>\n            F)\n            <jats:italic>\n              <jats:sub>a<\/jats:sub>\n            <\/jats:italic>\n            (PO\n            <jats:sub>4<\/jats:sub>\n            )\n            <jats:italic>\n              <jats:sub>b<\/jats:sub>\n            <\/jats:italic>\n            , which is found suitable for forging sulfur-fluorine and carbon-fluorine bonds.\n          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