The synthesis of well-defined imidazolium-based poly(ionic liquid)s (PILs) copolymers by nitroxide mediated polymerization (NMP) is reported. The viability of three different synthetic pathways to achieve poly[1-(4-vinylbenzyl)-3-butylimidazolium bis(trifluoromethylsulphonyl)-imide-co-methyl methacrylate] (poly(VBBI+TFSI--co-MMA)) was explored including direct polymerization of the ionic liquid monomer (VBBI+TFSI-) and post functionalization of precursor polymer poly(4-vinylbenzyl imidazole-co-methyl methacrylate). PILs with well-controlled molecular weight and low dispersity ((M) over bar (w) over bar /(M) over bar (n) over bar < 1.3) were obtained via all routes. A full synthetic, kinetic, and compositional comparison between methods is reported. These results illustrate an effective route for the synthesis of well-defined, pseudo-living functional PIL-methacryalte copolymers with tunable properties through potential methacrylate monomer substitution.