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Heat‐resistant polymer materials have been widely used in many fields, but their anticounterfeit is still a significant challenge. This work has successfully constructed a heat‐resistant polymer material that can achieve self‐anticounterfeit. In response to changes in the external environment, the color of polymer changes from yellow‐green to red reversibly, which is due to the fact that polymer material's backbone undergoes isomerization. Therefore, this high‐performance polymer material can not only be used in a high‐temperature environment for a long time but also achieve its anticounterfeit and be used in advanced security applications. [ABSTRACT FROM AUTHOR]