Rigid macroporous polymers developed in the early 1990s are widely used as efficient stationary phases for all types of chromatographic separations. The main advantages of so-called monolithic supports are their high hydraulic permeability and the dominance of the convection over the diffusion mechanism of mass-exchange under dynamic conditions that allow the separation to be carried out at extremely high flow rates and, consequently, during very short operation times. Among other types of macroporous polymers, the methacrylate-based monolithic materials represent the most popular and successfully explored class of sorbents. This review is an attempt to collect together the contributions of different groups working in the area of monolith preparation. Examples of different methcrylate monomers and crosslinkers, as well as porogenic solvents, including polymer ones, used in monolith preparation are discussed.