The construction and transportation sectors are major global energy consumers, making intelligent opto-thermal regulation of building envelopes and vehicle windows crucial for energy conservation and human comfort. Electrochromic windows hold significant potential, yet conventional technologies face scalability and cost barriers. Reversible metal electrodeposition offers a promising alternative due to its unique capability to efficiently control opto-thermal transmittance. However, symmetric dual-electrode RME architectures, essential for uniform optical switching, suffer from operational instability caused by voltage-driven parasitic reactions. Herein, we introduce an innovative strategy integrating redox mediators into EC dynamic windows to overcome this limitation. Using PEDOT:PSS in Cu/Bi-based RME hydrogel systems, we demonstrate accelerated interfacial kinetics and reduced overpotential, lowering the operational voltage from -1.9 V to -1.2 V while enhancing long-term stability (18,000 s vs. 180 s). The RM-engineered windows achieve 6,000 cycles without degradation, maintain stable optical modulation, and exhibit faster switching speeds. Importantly, this approach universally improves performance in traditional EC systems, such as tungsten oxides and viologen derivatives, establishing a material-agnostic platform technology. This RM strategy provides a unified design paradigm for scalable fabrication of next-generation dynamic glazing.

Electrochromism;Redox Mediator;Smart Glass