A FeCrAl alloy was preoxidized to form a protective alumina scale, and the effect of KCl deposits on the alumina scale was investigated while exposed during 1 and 24 h at 600 °C. However, impurity concentrations in the alumina scale change the ion conductivity and hence affect its protective properties. Therefore, Auger electron spectroscopy and time-of-flight secondary ion mass spectrometry were used to characterize the alumina scales and detect traces of K and Cl. The results showed that K and Cl existed as large sharp-edged crystals surrounded by a dendritic network after 1 h. However, after 24 h, those were dissolved, and K together with Cl was detected only in the outer layer of the duplex alumina scale, which was formed during preoxidation.