Hot-isostatically pressed silicon oxynitride (Si2N2O) ceramics free from sintering aids were oxidized in 1 atm dry oxygen at 1100 and 1300°C. The structural and chemical characteristics of the oxide and the nature of the oxide-Si2N2O interface were determined using cross-sectional transmission electron microscopy in conjunction with small-probe energy dispersive X-ray analysis and selected-area electron diffraction. Oxidation of Si2N2O resulted in the formation of amorphous SiO2. The oxide-Si2N2O interface was chemically abrupt. The interface was very flat when parallel to low-index, high atomic density Si2N2O crystal planes but became notably undulated if oriented to high index, low atomic density planes. About 6 vol% residual SiO2 phase was present in the bulk of the Si2N2O ceramics. Current results have provided an important baseline for the understanding of the oxidation behaviour of Si2N2O.