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Although fluorinated porous materials are considered promising candidates due to their high porosity, low density and acid and alkali resistance, they still face several challenges, such as complex preparation methods, heat‐induced polymerization of fluorinated emulsion taking too long and material brittleness. In this study, we avoided the difficult problem of stability of fluorine‐containing emulsions. We prepared functional hydrophobic hyperelastomers with morphological control, excellent oil absorption and recyclability by thiol–ene click photopolymerization using a water‐in‐oil high internal phase emulsion as template. The oil absorption capacity of the B4‐30%Si sample did not change after 10 recycles. By combining the advantages of organic fluorine and inorganic silicon, the prepared foam retains hydrophobicity and excellent chemical resistance, and has excellent structural and mechanical properties and can be compressed up to a 90% strain without rupture. Finally, the composite porous material B4‐30%Si has greater thermal stability (up to 280 °C) than commercially available polypropylene separators, due to the introduction of fluorine and silicon, and better flexibility and mechanical strength than glass fiber separators. Therefore, these materials are promising for use in lithium–sulfur batteries and wearable electronic components after further modification. © 2023 Society of Chemical Industry. [ABSTRACT FROM AUTHOR]