Cationic imidazolium‐functionalized polyethylene is accessible by insertion copolymerization of ethylene and allyl imidazolium tetrafluoroborate (AIm‐BF4) with phosphinesulfonato palladium(II) catalyst precursors. Imidazolium‐substituted repeat units are incorporated into the main chain and the initiating saturated chain end of the linear polymers, rather than the terminating unsaturated chain end. The counterion of the allyl imidazolium monomer is decisive, with the chloride analogue (AIm‐Cl) no polymerization is observed. Stoichiometric studies reveal the formation of an inactive chloride complex from the catalyst precursor. An effect of moderate densities (0.5 mol%) of ionic groups on the copolymers' physical properties is exemplified by an enhanced wetting by water.
