A broad spectrum of applications of "Salen"-based Schiff bases tagged them as versatile multifunctional materials. However, their applicability is often bounded by a temperature threshold and, thus, they have rarely been used for high temperature applications. Our investigation of a classical Schiff base, N,N'-bis(4-hydroxysalicylidene)ethylenediamine (L2), reveals that it displays an intriguingly combative response to an elevated temperature/fire scenario. L2 resists and regulates thermal degradation by forming an ablative surface, and acts as a thermal shield. A polycondensation via covalent cross-linking, which forms a hyperbranched cross-linked resin is found to constitute the origin of the ablative surface. This is a unique example of a resin formation produced with a Schiff base, that mimicks the operational strategy of a high-heat resistant phenolic resin. Further applicability of L2, as a flame retardant, was tested in an engineering polymer, polyamide-6. It was found that it reinforces the polymer against fire risks by the formation of an intumescent coating. This paves the way for a new strategic avenue in safeguarding polymeric materials toward fire risks. Further, this material represents a promising start for thermal protective applications.