This study presents our progress on using imidazolium-based polymerizable ionic liquids (Poly-ILs) in the NFW process to prepare polyionic biocomposites. Two novel Poly-ILs containing the 1-alkyl-3-vinylimidazolium cation and an alkylphosphonate anion were synthesized and subsequently characterized using NMR. Each Poly-IL was evaluated for its ability to (i) polymerize and (ii) solubilize a biopolymer (cellulose) matrix, and optimized parameters yielded polyionic biocomposite materials whose physicochemical properties were evaluated using ATR-FTIR, RAMAN, and SEM.