Porous polymer monoliths are a new category of materials developed during the last decade. These materials are prepared using a simple molding process carried out within the confines of a closed mold. Polymerization of a mixture that typically contains monomers, free-radical initiator, and porogenic solvent affords macroporous materials with large through-pores that enable flow-through applications. The versatility of the preparation technique is demonstrated by its use with hydrophobic, hydrophilic, ionizable, and zwitterionic monomers. The porous properties of the monolith can be controlled over a broad range. These, in turn, determine the hydrodynamic properties of the devices that contain the molded media. Since all the mobile phase must flow through the monolith, the mass transport within the molded material is dominated very much by convection, and the monolithic devices perform well even at very high flow rates. The applications of monolithic materials are demonstrated on the chromatographic separation of biological compounds and synthetic polymers, electrochromatography, gas chromatography, enzyme immobilization, molecular recognition, and in advanced detection systems. Grafting of the pore walls with selected polymers leads to materials with completely changed surface chemistries.