[reaction: see text] Monolithic polymer supports and scavengers were prepared via nucleophilic displacement of chlorine in poly(4-vinylbenzyl chloride-co-divinylbenzene) PolyHIPE materials. Reactions of monolithic PolyHIPE with tris(2-aminoethyl)amine, 4-aminobutanol, tris(hydroxymethyl)aminomethane, morpholine, and hexamethylenetetramine led to functionalized polymers with amino and hydroxy functionalities with high degrees of conversion. 4-Chlorobenzoyl chloride was efficiently and rapidly scavenged from solution by the tris(2-aminoethyl)amine derivative of monolithic poly(4-vinylbenzyl chloride-co-divinylbenzene) PolyHIPE at ambient temperature.