The production and use of [18F]fluoromethyl triflate ([18F]CH2FOTf), a more reactive [18F]fluoromethylating agent than [18F]fluoromethyl bromide ([18F]CH2BrF), is described. [18F]CH2FOTf was prepared from [18F]CH2BrF. The latter was synthesized by nucleophilic substitution of CH2Br2 with no-carrier-added [18F]fluoride and purified by four Sep-Pak Plus silica cartridges connected in series. It was then quantitatively converted on-line to [18F]CH2FOTf by passing through a heated AgOTf column. Decay-corrected radiochemical yields of [18F]CH2FOTf based on [18F]fluoride were 47 +/- 8% (n = 20). Both [18F]CH2BrF and [18F]CH2FOTf were applied to solid-supported [18F]fluoromethylation of N,N-dimethylaminoethanol on a Sep-Pak Plus C18 cartridge to produce the 18F-labeled choline analogue, (beta-hydroxyethyl)dimethyl-[18F]fluoromethylammonium ([18F]fluorocholine). Depending on flow rate and amount of precursor used, decay corrected radiochemical yields of [18F]fluorocholine from [18F]CH2BrF ranged from 6% to 63%, while [18F]CH2FOTf afforded yields of more than 80%. Thus, by using the latter reagent and a subsequent purification on a Sep-Pak Accell CM cartridge, [18F]fluorocholine was produced from [18F]fluoride in overall radiochemical yields of 40% (decay corrected) in less than 30 min.