A procedure for the radiosynthesis of aliphatic [¹⁸F]trifluoromethyl groups by reacting 1,1-difluorovinyl precursors with [¹⁸F]fluoride ions, resulting in the equivalent of direct nucleophilic addition of H[¹⁸F]F, has been developed. A variety of ¹⁸F-labelled model compounds were then obtained and two potential [¹⁸F]radiotracers were synthesised by a two step process starting from 1,1-difluorovin-2-yl 4-toluenesulfonate. The method is widely applicable for the synthesis of novel radiotracers in high radiochemical yields and good specific activity.