In this article, we report a novel high-efficiency electrochemical capacitor using PANI-PAAMPSA films on thermally stable UV-curable thiolene-based substrates. For the first time, surface modification of the thiolene polymer-based substrates via O-2 plasma prior coating was employed in combination with a conducting polymer, resulting in significant improvements in adhesion and uniformity of PANI-PAAMPSA films. Novel supercapacitors using PANI-PAAMPSA coated on plasma-treated thiolene-based polymer substrates exhibited a significant maximum specific capacitance of 42 Fg(-1). This work could open up opportunities for water-soluble PANI-PAAMPSA and thiolene-based polymer substrates in various areas, such as solution-based energy-storage and light-weight functional devices in the very near future.