A series of functionalised imidazolium halide salts with substituents able to form π‐bonds have been prepared and characterised. Subsequent reaction of these imidazolium halides with Ag[C(CN)3] affords imidazolium‐based ionic liquids (ILs), some of which are characterised by extensive π–π interactions between the cation and [C(CN)3] anion. The conductivities of the room temperature ILs with the [C(CN)3] anion were determined and the IL with an alkene functionality exhibits the highest conductivity, exceeding that of 1‐ethyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide, a commonly used IL electrolyte. No clear correlations between the extent of π–π interactions and the conductivities were observed.