DNA is often referred to as the molecule of life, since it contains the instructions for making the required proteins. However, it is not simply a (genetic) code to be read; its structure has an important role in determining when and how much of a particular 5 protein is made at any point in time. Furthermore, there are a range of special DNA structures, e.g. Holliday junctions, which play essential roles for the existence of life as we know it or as it will become. In this tutorial review the normal B-DNA structure is summarised and metallomolecule binding modes discussed then used as a basis for examining DNA structures which can be induced by molecules containing metallic cations. The effects of aquated metal ions, cobalt ammine and ruthenium octahedral metal complexes, metallo helicates and platinum complexes such as cis-platin are discussed alongside techniques such as NMR, 10 X-ray crystallography, gel electrophoresis, circular dichroism, linear dichroism and molecular dynamics.