A broad variety of monolithic macroporous polymers with both controlled chemistry and porous properties was prepared using UV-initiated free-radical polymerization. The chemistry of the monoliths is defined by the composition of the monomer mixture used for the polymerization. The use of functional methacrylate monomers such as glycidyl methacrylate, 2-hydroxyethyl methacrylate, butyl methacrylate, 2-acrylamido-2-methyl-1-propanesulfonic acid, and [2-(methacryloyloxy) ethyl] trimethylammonium chloride enabled the preparation of monoliths with reactive, hydrophilic, hydrophobic, and ionizable functionalities, respectively. The porous properties of these monoliths were mainly affected by the choice of the porogenic solvent system. Because the UV polymerization was carried out at room temperature, even low molecular weight alcohols and other low boiling point solvents could safely be used to create a versatile series of binary porogenic mixtures. Monoliths were prepared in spatially defined positions using the photolithographic technique within a fused silica capillary and on microfluidic chips, and the former was demonstrated with the separation of derivatized amines by means of capillary electrochromatography in the reversed-phase mode. Similarly, a monolith prepared in the microchip format was used to demonstrate a microextraction with enrichment of a solution of green fluorescent protein by a factor of 1000.