Monolithic materials were prepared via electron-beam curing from ethyl methacrylate, trimethylolpropane triacrylate, and norborn-5-ene-2-ylmethyl acrylate. Reaction of the norborn-2-ene groups with either RuCl2(PCy3)2(CHPh) (1) or RuCl2(PCy3)(1,3-dimesityl-4,5-dihydroimidazol-2-inylidene)(CHPh) (2) resulted in the surface attachment of the initiators. The extent of initiator immobilization was found to be substantially higher for 1 than for 2. Reaction of the surface immobilized initiators with various monomers resulted in the desired surface modification of EB-derived monoliths. The amounts of grafted monomer were determined by elemental analysis and ICP-OES.