The synthesis of PEGylated polymerized high internal phase emulsions (PolyHIPE) using commercially available poly(ethylene glycol) methacrylate (PEGMA), employing oil-in-water (o/w) HIPEs for the preparation of polyacrylamide and PolyHIPE beads, was investigated. The reverse HIPEs are found to be fairly unstable over time, and large voids could be seen after curing due to oil droplet coalescence. It is observed that PEGylated PolyHIPEs recover their original shape and pore structure, such that it can be used for reversible immomabilization of elastin-based side-chain polymers (EBP) upon rewetting. The soaking of PolyHIPE in pH 3.2 buffer solution, washing, and filtering shows that no fluorescence is detected on the surface of the monolith. The results also show that the ability of EBPs to undergo cooperative assembly has been exploited to enable the reversible immobilization of complementary EBPs from solution onto the surface of the porous material.