Using a high internal phase emulsion templating approach, highly porous open cellular polymers are prepared from divinyl adipate (DVA). The morphological structure of the monoliths includes cavities in the diameter range of around 5–25 μm and secondary interconnecting pores approximately 1 μm in diameter. A high interconnectivity of the cavities and a porosity of up to 85% are achieved. Using an elevated temperature of the aqueous phase during the emulsion preparation and controlled ageing of emulsions, the influence on pore size is investigated. Porous poly(DVA) can be degraded in a basic aqueous medium via the cleavage of ester bonds, the medium influencing the kinetic profile of degradation. image