Bidirectional Color Switching and Multimodal Energy Outputs Enabled by Synergistic Complementary Color Fusion and Inherent Potential Gradient in a Fully‐Printed Tri‐Electrode Electrochromic System

ABSTRACT Self‐powered electrochromic devices, which integrate optical modulation with energy storage, represent a significant direction in adaptive optics and smart electronics. However, they still face limitations such as monotonous operation modes, slow self‐charging, and complex fabrication processes. To address these challenges, we present a novel self‐powered electrochromic system (MnO 2 ||PEDOT:PSS/PANI:PSS||Zn) based on a synergistic strategy of complementary color fusion and potential gradient utilization. The electrochromic electrode exploits the complementary color fusion effect between the cathodic electrochromic material PEDOT:PSS and the anodic electrochromic material PANI:PSS, enabling distinct color manifestations (green, purple, and blue) at different redox states. The inherent potential gradient among MnO 2 , PEDOT:PSS/PANI:PSS, and Zn provides a robust driving force for the redox reactions in the electrochromic electrode, allowing the system to achieve rapid and reversible bidirectional color switching along with multiple output modes. Via a fully‐printed fabrication process, we integrated the three electrodes onto a single paper substrate, constructing a compact, mechanically flexible, multi‐mode self‐powered electrochromic system. This system has been successfully applied in reconfigurable multicolor display arrays and pressure‐activated connected smart display labels. We envision that this work provides new insights into the development of flexible, multifunctional energy‐optical systems.