Characterisation of uranium oxides in different conditions is a challenge both in nuclear and environment sciences. We focus here on U4O9, which is a superstructure of UO2. Homogeneous U4O9 powder was fabricated and characterised by Raman spectroscopy. The Raman spectrum of a pure-phase U4O9 is, for the first time, completely described and interpreted. U4O9 Raman spectrum derives from the well characterised one of UO2. Besides reminiscent modes of UO2, a band at 630 cm-1, which has a specific response to polarised light, was interpreted as characteristic of clusters of interstitial oxygen atoms. These experimental data will help to rationalise the interpretation of UO2 damaged samples. Copyright © 2011 John Wiley & Sons, Ltd.