Introduction 1,2,3-Triazoles are incredibly popular molecular motifs that have found widespread application in a diverse range of fields, including material science, bioconjugation, drug design, catalysis and supramolecular chemistry. One reason for the use of 1,2,3-triazoles in these fields is their high chemical, thermal and biological stability, however they can also perform important functions. For example, 1,2,3-triazoles have been applied as metabolically-stable bioisosteres for amides, esters, carboxylic acids, alkenes and other heterocycles; whilst their high hole affinity and H-bond donor properties have led to applications in electronics and anion recognition, respectively. The immense range of applications of 1,2,3-triazoles can be also attributed to the ease of their synthesis through the Nobel Prize winning Cu-catalysed azide-alkyne cycloaddition reaction. In contrast to the thermal Huisgen azide-alkyne cycloaddition, the Cu-catalysed variant provides excellent yield and regioselectivity for 1,4-substituted triazoles, and can be performed at room temperature in a range of solvents, including water, allowing it's use in bioconjugation applications. Bis-triazole/triazolium scaffolds as halogen/chalcogen bond donors in anion binding and catalysis have recently received significant attention and application. As part of an on-going program into the design of new chalcogen bond donors, we were interested in the synthesis and functionalisation of related bis-triazoles bearing electron-withdrawing N-substituents (Figure ). Using conditions developed by Huber, the literature synthesis of selenated bis-triazole 3 bearing N-octyl substituents was replicated in an excellent 77% yield (Figure ); however, applying these conditions to a bis-triazole bearing Nbis(trifluoromethyl)phenyl groups resulted in a complex mixture, with none of the expected product 4, or starting material 2, present. Only a small number of studies have previously focused on the lithiation-functionalisation of triazoles (Figure ). This is surprising considering 1,4,5-functionalised triazoles are bioactive motifs, and post-functionalisation of 1,4-triazoles in the 5-position provides a useful new vector to add or improve function in any of the myriad of applications for which triazoles find use. In 1971, Raap reported the lithiation of 1,4-diphenyl-1,2,3-triazole, followed by reaction with methyl iodide or carbon dioxide. Rapp also demonstrated that the lithiated triazole intermediate was prone to decomposition above 10 °C, resulting in extrusion of N2 and formation of an N-phenylketenimine anion. Ohta subsequently demonstrated an expanded electrophile scope for the lithiation-functionalisation of N-methyl-1,2,3triazole, whilst Holzer and Begtrup have reported directed lithiations using N-alkoxymethyl-and N-benzyloxy-1,2,3-triazole, Electron-neutral/donating N-substituents (Raap, Ohta) respectively. The synthesis of 1,4,5-functionalised triazoles can also be achieved through 'interrupted' Cu-catalysed azidealkyne cycloaddition reactions, however these methods add complexity by requiring alignment of the relative rates of various processes and therefore can restrict substrate scope. Due to the lack of studies on the lithiation-functionalisation of 1,2,3-triazoles bearing electron-withdrawn N-substituents, we focused our efforts on understanding and optimizing this process. Herein, we report the lithiation-deuteration of a selection of 1,2,3-triazoles bearing electron-withdrawing groups to assess the regioselectivity of lithiation and understand the stability of the lithiated intermediates. The optimised lithiation conditions were then applied in lithiation-functionalisation reactions using a range of electrophiles (Figure ).