AbstractSummary: An oil‐in‐water high internal phase emulsion consisting of acrylic acid, water, and a crosslinker (N,N′‐methylene bisacrylamide) as the water phase, and toluene as the oil phase was successfully stabilised to sustain thermal initiation of radical polymerisation resulting in porous open‐cellular monolithic material. The type of initiator used influenced the average pore size ranging from approx. 708 nm to approx. 1 087 nm, as determined by mercury porosimetry.Schematic of the preparation of an oil‐in‐water‐type polyHIPE (high internal phase emulsion).imageSchematic of the preparation of an oil‐in‐water‐type polyHIPE (high internal phase emulsion).