Two new butterfly-shaped monomers TTCQF and TTCQH consisting of camphor-substituted quinoxaline units as π-spacers were designed and synthesized, which were further electrochemical polymerized and deposited on ITO substrates for electrochromic energy storage devices. The present cross-linked polymer thin films PTTCQF and PTTCQH displayed prominent color changes with significant optical contrast in both the visible and near-infrared regions under external electrical stimuli. These two polymers showcased superior electrochromic performance, involving high optical contrast, fast switching speed, and good coloration efficiency. Additionally, both polymers demonstrated a high areal specific capacitance (12 mF/cm2 for PTTCQH and 9.97 mF/cm2 for PTTCQF) at a current density of 0.1 mA/cm2. Electrochromic energy storage devices based on these polymers were fabricated, and not only illuminated an LED bulb but also visually indicated the energy storage state, guaranteed their potential for applications in energy-saving smart windows. This work may provide valuable insights into the development of efficient cross-linked electrochromic energy storage polymers.