[Fe(1,10‐phenanthroline)3]2+ is known to racemise in solution and DNA is known to shift the equilibrium point of the Δ/Λ‐[Fe(1,10‐phenanthroline)3]2+ mixture from 50:50 to a position favouring a slight excess of the Δ enantiomer. In this paper it is shown that DNA catalyses the racemisation reaction, presumably by providing vibrational energy to species that bind in a less favoured mode for that enantiomer. The racemisation of [Co(1,10‐phenanthroline)3]3+, however, is not enhanced by DNA unless [Co(1,10‐phenanthroline)3]2+ is also added to the solution. In this case, the DNA acts as a template to facilitate the CoII ↔ CoIII electron transfer. Racemisation occurs while the [Co(1,10‐phenanthroline)3]n+ is in the labile CoII form.