In conclusion, we have demonstrated that 5-lithiated 1,2,3triazoles with N-aryl substituents bearing electron-withdrawing groups are susceptible to decomposition, even at -78 °C. In addition, lithiation can take place competitively on both the triazole and the electron-withdrawn N-aryl ring. To achieve successful and regioselective lithiation-functionalisation processes, short reaction times and low reaction temperatures are essential. In total, the lithiation of 9 triazoles and the use of 9 different electrophiles was demonstrated, giving 5-functionalised triazoles in 23-67% yield. Whilst LDA was used for the lithiation of the majority of triazoles, the lithiation of an Npentafluorophenyl triazole resulted in competitive orthoamination, presumably through directed nucleophilic aromatic substitution. The use of the more sterically-hindered LiTMP was therefore required in this case. Furthermore, we have demonstrated that even at -78 °C lithiated triazoles bearing an N-trifluoromethyl substituent are not sufficiently stable to be utilised. This experimentally-determined trend of lithiated triazole intermediate stability is in line with computational predictions made by Ariafard on an analogous series of cuprated triazole intermediates in Cu-catalysed azide-alkyne cycloaddition reactions. Overall, this work provides insight into the stability of metalated triazole intermediates and presents cautionary information and suggested solutions for the successful functionalisation of triazoles bearing electron-withdrawn Nsubstituents.