<p dir="ltr">We have developed a method for the radiochemical synthesis of 18F-ployfluorinated small molecules from alkyl halide and [18F]fluoride mediated by silver(I) oxide. The reaction is demonstrated on a broad substrate scope.</p><p dir="ltr">This data set contains 1H, 19F and 13C NMR data files for the characterisation of the non-radioactive compounds.</p><p dir="ltr">An appropriate NMR processing software is required for raw NMR data files</p>