The properties of a metal coordination complex are determined as much by the ligand set – the molecules and ions coordinated to the metal centre – as by the nature of the metal itself. The design and use of new ligands is consequently a major part of chemical research. This review considers the role of multifunctional ligands in three separate and distinct areas of chemistry. In homogeneous catalysis, the role of hybrid and hemilabile ligands is considered, and the introduction of functionalities designed to overcome problems of separation, either by tethering or solubilising, is discussed. In supramolecular chemistry, functionalities enabling the recognition and sensing of cations and anions are examined. In addition, ligands containing two or more faces are discussed for their role in metallodendrimer formation and self-assembly reactions, and the use of bifunctional ligands in crystal engineering is addressed. The application of metal complexes in medicine is examined by consideration of cis-platin and its derivatives as antitumour agents. Imaging agents are also discussed with the uses of gadolinium MRI contrast agents and γ-emitting technetium complexes highlighted.