[18F]Bromofluoromethane was synthesised from dibromomethane by substitution of bromine with [18F]fluoride. The synthesis and separation of the [18F]bromofluoromethane were automated. [18F]Bromofluoromethane was used to convert a phenolic and a thiophenolic precursor into a labelled ether and thioether, respectively. The specific radioactivity of these labelled products was determined with both high-performance liquid chromatography (with UV-absorbance detection) and liquid chromatography (with mass spectrometric detection). The median for the specific radioactivity, corrected at the end of radionuclide production, was 934GBq/micromol (range 40-9900 GBq/micromol; n = 83).