Abstract: Appropriately chosen metallomonomers enable BINOL-shaped cavities (both matched and mismateched) and non-chiral cavities to be associated with the (S-MeOBiphep) PtCl2 precatalyst by molecular imprinting process. Each of the three polymers contains a polymerizable P2PtCl2, distinguished only by the shape of the associated cavity. Activation of molecularly imprinted metal complexes generates Lewis acid catalysts for the glyoxylate-ene reaction. We will present the catalysis experiment demonstrating that the cavity and chiral diphosphine ligands control the stereochemistry of poisoning by chiral BINAM ligands and the selectivity of the –ene catalysis, respectively.