2-[¹⁸F]Fluoroethyl azide ([¹⁸F]FEA) can readily be obtained by nucleophilic substitution of 2-azidoethyl-4-toluenesulfonate with [¹⁸F]fluoride (half-life 110 min), and has become widely used as a reagent for 'click' labeling of PET tracers. However, distillation of [18F]FEA is typically required, which is time-consuming and unpractical for routine applications. In addition, copper(I)-catalyzed cycloaddition of [¹⁸F]FEA with non-activated alkynes, and with substrates containing labile functional groups, can be challenging. Herein, we report a highly efficient and practical ligand-accelerated one-pot/two-step method for 'click' labeling of small molecule tracers with [¹⁸F]FEA. The method exploits the ability of the copper(I) ligand bathophenanthrolinedisulfonate to accelerate the rate of the cycloaddition reaction. As a result, alkynes can be added directly to the crude reaction mixture containing [¹⁸F]FEA, and as cyclisation occurs almost immediately at room temperature, the reaction is tolerant to labile functional groups. The method was demonstrated by reacting [¹⁸F]FEA with a series of alkyne-functionalized 6-halopurines to give the corresponding triazoles in 55-76% analytical radiochemical yield.