Abstract: Separation of a variety of analytes that are polar, nonpolar and ionic using functionalized polymeric media is disclosed. Preformed rigid particles of highly crosslinked homopolymer of polyvinylidene compounds are functionalized using the residual vinyl groups onto which monovinyl compounds are covalently bonded through polymerization. The functionalization imparts desirable surface properties for separation applications such as liquid chromatography and solid phase extraction.