Molecular magnetism relies on the ability of the synthetic chemist to make an enormous breadth of structurally diverse polymetallic cages spanning the d- and f-block of the periodic table. The structural and magnetic characterisation of such species details the magneto-structural relationship and often uncovers fascinating magnetic phenomena which, in turn, feedback into the synthesis of new complexes designed to enhance and improve properties toward application. Synthetic strategies for the design of polymetallic clusters containing multiple paramagnetic metal ions span the range from serendipitous self-assembly in which coordinatively flexible metal ions, that can often exist in multiple oxidation states, are combined with organic ligands capable of bridging in numerous ways to form complexes whose absolute structures are difficult to predict, through to a more supramolecular approach whereby metal ions with defined coordination geometries are paired with rigid ligands containing donor atoms with a single, predesigned orientation preference that affords, in most cases, a predicted structure. In this lecture I will highlight a variety of methods for making such species, demonstrating how structural manipulation can be used to tune magnetic behaviour.