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This work presents a new strategy to achieve highly stable electrochromic devices and bilayer film construction. A novel solution‐processable electrochromic polymer P1‐Boc with quinacridone as the conjugated backbone and t‐Boc as N‐substituted non‐conjugated solubilizing groups is designed. Thermal annealing of P1‐Boc film results in the cleavage of t‐Boc groups and the formation of N─H⋯O═C hydrogen‐bonding...