The FSW-0 recoverable satellite used wood as its heat-shield
A novel feature of the spacecraft's re-entry module was the use of impregnated oak, a natural material, as the ablative material for its heat shield.
(year: 1974)
https://en.wikipedia.org/wiki/Fanhui_Shi_WeixingOpen linkView original on mander.xyz
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Pineapple skin is also quite wild: https://twistedsifter.com/2024/09/pineapple-skin-can-withstand-heat-over-1000-degrees-celsius/