Over several years, our research team has contributed to ligand design for metal-catalyzed stereoselective transformations. This has been achieved with the synthesis and application to organic transformations of interest of an array of structurally diverse P-containing ligands. These range from highly modular enantiopure phosphine–phosphite ligands to supramolecularly regulated enantioselective phosphorus-based catalysts. Our research in supramolecular interactions has also led to the discovery of an unprecedented halogen-bonded rhodium-catalyst.