Monolithic polymeric materials are prepared via ring-opening metathesis copolymerization of norborn-2-ene with 1,4,4a,5,8,8a-hexahydro-1,4,5,8-exo,endo-dimethanonaphthalene in the presence of macro- and microporogens, that is, of n-hexane and 1,2-dichloroethane, using the Schrock catalyst Mo(N-2,6-(2-Pr)2-C6H3)(CHCMe2Ph)(OCMe3)2. Functionalization of the monolithic materials is accomplished by either terminating the living metal alkylidenes with various functional aldehydes or by post-synthesis grafting with norborn-5-en-2-ylmethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoate. Finally, boronate-grafted monolithic columns (100 x 3 mm i.d.) are successfully applied to the affinity chromatographic separation of cis-diol-based biomolecules.