Novel lithium polyelectrolyte-ionic liquid systems, using poly(lithium 2-acrylamido-2-methyl propanesulfonate) and its copolymer with N-vinyl formamide, have been developed in this work. The ionic liquid used in this work is from a novel family of methanesulfonate ionic liquids, specifically N-hexyl-N,N,N-tributyl ammonium methanesulfonate, which is chosen because of the similarity with the anionic functionality of the polymer. The ionic liquid thereby acts as a good solvating medium for the polyelectrolyte. It was found that the copolymer-based polyelectrolyte-ionic liquid system exhibits two to three times higher conductivity than that of the homopolymer system. The results of solid-state Li-7-NMR have shown that lithium cations in the copolymer system are mobile whereas in the homopolymer, only a fraction appears to be mobile even at 80 degreesC. This supports the hypothesis that separation of the charged groups on the polymer backbone via the co-monomer encourages the dissociation of lithium cations from the sulfonate groups bonded to the polymer chains, and hence, results in an increase in conductivity of the polyelectrolyte material.