Presented are the formation of iron oxide layers on evaporator tubes in an actual fossil power plant operated under all volatile treatment (AVT) condition and an experimental simulation of iron oxide formation in the presence of ferrous and ferric ions. After actual operations for 12781 and 36326 hr in the power plant, two iron oxide layers of magnetite on the evaporator tubes were found: a continuous inner layer and a porous outer layer. The experimental simulation (i.e., artificial corrosion in the presence of ferrous and ferric ions at 100 ppm level for 100 hr) reveals that ferrous ions turn the continuous inner oxide layer on tube metal to cracks and pores, while ferric ions facilitate the production of porous outer oxide layer consisting of large crystallites. Based on a comparison of the oxide layers produced in the experimental simulation with those observed on the actually used tubes, we propose possible routes for oxid