The use of anion-exchange resins to separate and purify plutonium from various sources represents a major bottleneck in the throughput that can be achieved when this step is part of a larger separation scheme. Slow sorption kinetics and broad elution profiles necessitate long contact times with the resin, and the recovered Pu is relatively dilute, requiring the handling of large volumes of hazardous material. In this work, high internal-phase emulsion (HIPE) foams were prepared with a comonomer containing a dormant nitroxide. Using surface-initiated nitroxide-mediated polymerization, the foam surface was decorated with a brush of poly(4-vinylpyridine), and the resulting materials were tested under controlled flow conditions as anion-exchange media for plutonium separations. It was found that the grafted foams demonstrated greater ion-exchange capacity per unit volume than a commercial resin commonly used for Pu separations and had narrower elution profiles. The ion-exchange sites (quaternized pyridine) were exposed on the surface of the large pores of the foam, resulting in convective mass transfer, the driving force for the excellent separation properties exhibited by the synthesized polyHIPE foams.