The achievement of high ionic conductivity in new “polymeric ionic liquids” (PILs) is of great interest as it refers to the solid state electrolytes and their applications in electrochemistry. Four ionic monomers, including two new ones, namely N-[(2-methacryloyloxy)-propyl]-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide (M1), 1-[2-(methacryloyloxy)propyl]-3-methylimidazolium bis(trifluoromethylsulfonyl)amide (M2), N-methyl-N-ethylpyrrolidinium(3-sulfopropyl) methacrylate (M3), and 1-methyl-3-ethylimidazolium(3-sulfopropyl) methacrylate (M4), were prepared and used both for the synthesis of linear PILs and ionic networks with poly(ethylene glycol) dimethacrylate (PEGDM). The optimal polymerization conditions for obtaining high molar mass PILs (MsD up to 1.24 × 106 g/mol) were identified. The copolymerization of oppositely charged monomers was studied as well. Polycations, polyanions, and their random ionic copolymers were compared in terms of their physical properties. The examined properties were fo