The poor burning resistance of cotton necessitates the control of its pyrolytic reactions, but many approaches have relied on the use of synthetically engineered chemicals. Herein, we show how a natural polyphenol from plants—tannic acid—acts with sodium ions to create a robust thermal barrier coat on cotton, with a focus on thermal kinetics. The kinetic information, combined with thermal and spectral analyses, revealed that the outer layer of galloyl units in tannic acid decomposes via a two-step reaction, producing a multicellular char of crosslinked aromatic rings, followed by the blowing of carbonaceous cells into a further expanded structure.