A study has been made of the electrical characteristics and optical emission spectra exhibited when discharge events take place during plasma electrolytic oxidation processing. Both conventional and small area experimental arrangements have been employed, allowing detailed measurement of durations, and temporal distributions, as well as such characteristics as charge transfer, and power. Individual discharges are of short duration, typically tens to hundreds of microseconds, but there is a strong tendency for them to occur in cascades that commonly last between several ms and several tens of ms. The composition, temperature and electron density of the plasma formed during PEO processing are inferred from characteristics of the emission spectra. This confirms that there are two distinct regions of plasma; a lower density peripheral region at~3500 K, and a higher density core at 16,000 ± 3500 K. The implications of these results are considered in terms of the interpretation of different types of experimental measurement, and attention is also briefly given to how such behaviour might relate to the mechanisms of growth.