The delineation of steric effects in the interaction of metal species with biomolecules has been addressed. More specifically, a focus has been placed on the interaction of platinum complexes with nucleoconstituents. Steric effects thus characterised have been related to the biological properties of such complexes. Steric aspects of metal complex speciation have been investigated both from experimental and theoretical viewpoints. Manipulation of steric effects within model systems has been carried out by way of judicious ligand design.