Molecular imprinting involves the self-assembled complexation of a substrate to functional monomers to form a pre-polymer complex which is “locked-in” to place by copolymerization with an excess of crosslinking monomer. Removal of the template leaves binding or catalytic sites that are complementary in size, shape, and functionality to the template. Most of the research in molecularly imprinted materials has focused on choice of substrate or functional monomer of the pre-polymer complex. The cross-linking monomers have primarily been EGDMA or DVB, which are commercially available. Redirecting focus on the design of crosslinking monomers for molecular imprinting, we have developed new classes of crosslinked polymers to optimize the performance of molecularly imprinted polymers. The design of the new crosslinking monomers has followed two strategies: (1) development of new crosslinked materials for formation of the supporting matrix, and (2) development of crosslinking monomers that simultaneously serve as the functional monomer. The details of the design, synthesis, polymerization and performance of these new crosslinking monomers for molecularly imprinted polymers will be reported.