Even in simple low-alloy steels the oxide scales that form during hot working processes are often a complex mixture of three iron oxide phases: haematite, magnetite and wustite. The mechanical properties, and hence descalability, are intimately linked with phase distribution and microstructure, which in turn are sensitive to both steel composition and oxidation conditions. In this study electron backscatter diffraction in the SEM has been used to characterize the microstructures of oxide scales formed on two compositions of low-alloy steel. The technique can unambiguously differentiate between the candidate phases to provide the phase distribution within the scale. This is used to investigate grain orientation relationships both within and between phase layers. It has been found that the strength of the orientational relationship between the magnetite and wustite layers is dependent on steel composition, and in particular Si content. In a low-Si (0.01 wt%) alloy only a very weak relationship was found to exist for a range of oxidation temperatures (800-1000 degrees C), whereas for the higher Si (0.37 wt%) alloy a strong relationship was observed under the same oxidation conditions. These orientational relationships are particularly important because, in this temperature range, the majority of oxide scale growth occurs at the magnetite/wustite interphase boundary.