Highly ordered rod-like polymeric monoliths with large-pores have been successfully synthesized using ionic liquids (ILs) IL-1 (1-Butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [BMIM][NTf2]) and IL-2 (1-octy1-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [OMIM][NTf2]) as alternative porogenic solvents. The presence of ILs can not only promote the formation of a highly ordered macroporous structure, control the morphology of the polymer and control the chemical composition of surfaces for monoliths prepared from DVB. In this regard, post-functionalization of the monoliths can be easily achieved using the functional monomers introduced in the polymerization process or the unreacted vinyl groups present in the polymeric matrix. This control has allowed the preparation of monolithic Supported Ionic Liquid-like Phases (m-SILLPs) with excellent morphological properties. These m-SILLPs have been studied as supports for large biomolecules. Bioadsorption studies show that the adsorbed amount of protein reaches values as high as 150-200 mg of protein per gram of support. (C) 2014 Elsevier B.V. All rights reserved.