In order to improve the efficiency of power generation system and reduce CO2 emissions power plants work at high temperature and pressure. Under such conditions modified steel 9Cr, which fulfils the requirements concerning creep resistance, is used. However, Cr2O3 formed on the steel does not protect the construction material in the atmosphere which contains CO2 and SO2. The aim of the experiment was to study the behaviour of P91 steel in CO2 atmosphere with the addition of 1% and 5 vol.% of SO2 at different temperatures (700, 800 and 900°C). It was concluded that the corrosion rate of P91 steel is increasing with a rise in temperature. Scales formed in CO2 atmosphere at 900°C contain a mixture of iron oxides in the outer layer and chromium-iron spinel in the inner layer. The FeS and Ni were found in the inner zone of scales formed in SO2 atmosphere.