The utility of several types of multimetallic asymmetric catalysts is reviewed. The appropriate design of multidentate chiral ligands provides homobimetallic, heterobimetallic, and polymetallic catalysts upon complexation with metal cations. Cooperative work of multiple catalytically active sites in the asymmetric multimetallic catalysts allows for enhanced catalytic activity and stereoselectivity over monometallic catalysts. Facile systematic tuning of the asymmetric multimetallic catalysts by manipulation of multidentate ligand structure and combination of metal cations enables the generation of diverse set of catalysts having distinct three-dimensional and catalytic properties, boosting the optimization process to identify the best catalyst for a specific reaction of interest.