A novel approach to acrylate/methacrylate-based monolithic systems via electron-beam (EB) initiated polymerization is described. The thus obtained monolithic columns were found suitable for the analytical scale separation of proteins. The novel concept of monolith synthesis was successfully extended to the synthesis of large diameter (20 mm × 300 mm id) monolithic columns applying EB irradiation in a pulsed mode. A homogeneous structure in terms of particle size and porous structure was again realized throughout the entire monolith. Functionalization of the monolithic columns was accomplished via copolymerization of a functional monomer, N,N-dipyrid-2-ylmethacryl amide. The thus obtained functional monoliths were loaded with Pd (II) and used for the Heck-coupling of styrene with iodobenzene in a continuous process.