The salt 1-(2,3,5,6-tetrafluoropyridyl)-3-benzylimidazolium bromide crystallizes in the non-centrosymmetric space group Pna2₁. The structure arises from π–π stacking between the benzyl and tetrafluoropyridyl groups of the cations and cation–bromide interactions. It is the latter that gives rise to the non-centrosymmetry.