A new facile and efficient route for the chemical functionalisation of thiol-acrylate polyHIPE materials with responsive macromolecules using the highly emissive dithiomaleimide (DTM) linker is demonstrated. Functionalisation is found to be reversible upon addition of a thiol-containing compound, glutathione, resulting in switchable surface properties including fluorescence and wettability, hence broadening the scope of applications.