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Foam thermal insulators are indispensable for prevailing energy‐saving engineering, however their widespread use brings intractability such as unsustainability, "white pollution", and fire hazards. The emergence of bio‐based foams is highly appreciated, but the fabrication approaches are economically unattractive and/or the product properties are inferior, making their large‐scale implementation unviable. Herein, a versatile, thermally remoldable phosphate‐containing polyurethane composite foam (LPU‐G) is constructed from natural lignin and expanded graphite flakes via an atmospheric pressure and scalable one‐pot strategy. The optimal LPU‐G exhibits exceptional mechanical strength, capable of supporting over 6000 times its weight without significant deformation. Moreover, the LPU‐G demonstrates the desired multifunctionality in handling extreme circumstances, including humidity‐tolerant thermal insulation, superb water vapor barrier, and withstanding ≈1200 °C flame without ignition. Based on the "expansion‐conductivity" micro‐mechanism, LPU‐G is the first foam material to be constructed as a sensitive fire alarm system with an ultra‐long alarm time (>1800 s). Surprisingly, LPU‐G can be rapidly upcycled into recyclable bulk composites for a second life through simple thermo‐molding processes rooted in the multi‐dynamic behavior of the phosphate, carbamate, and hydrogen bonds. The easy‐to‐scale LPU‐G represents a new generation of thermal insulators that address concerns regarding unsustainability, high cost, fire risk, and inferior mechanical properties. [ABSTRACT FROM AUTHOR]