Cation-polymerized ionic liquids and non-ionic polymer monomers can be facile to chain into performance-enhanced conducting copolymers in combination with their respective features. A novel highly-flexible Br-based polycationic conducting copolymer is presented that shows both wide electrochemical window (6.0 V) and high ionic conductivity (2.04 × 10−6 S·cm−1 at 25 °C, 3.09 × 10−4 S·cm−1 at 60 °C), capable of potential solid polymer electrolyte. A 4.2 V flexible all-solid-state C/C supercapacitor is evaluated by using the poly(VAc-co-...