Amino-functional macroporous monoliths from polymerized high internal phase emulsion (polyHIPE) were surface modified with initiators for atom transfer radical polymerization (ATRP). The ATRP initiator groups on the polyHIPE surface were successfully used to initiate activator regeneration by electron transfer (ARGET) ATRP of (meth)acrylic monomers, such as methyl methacrylate (MMA) or tert-butyl acrylate (tBA) resulting in a dense coating of polymers on the polyHIPE surface. Addition of sacrificial initiator permitted control of the amount of polymer grafted onto the monolith surface. Subsequent removal of the tert-butyl protecting groups yielded highly functional polyHIPE-g-poly(acrylic acid). The versatility to use the high density of carboxylic acid groups for secondary reactions was demonstrated by the successful conjugation of enhanced green fluorescent protein (eGFP) and coral derived red fluorescent protein (DsRed) using EDC/sulfo-NHS chemistry, on the polymer 3D-scaffold surface. The materials and methodologies presented here are simple and robust, thus, opening new possibilities for the bioconjugation of highly porous polyHIPE for bioseparation applications.