The structure of the scale formed on the surface of Fe - Cr - X alloys exposed to 1143K high sulfidation($Ps_2$ = 1.11$\times$$10^-7$ atm, $Po_2$ = 3.11$\times$$10^-20$ atm) or sulfidation/oxidation(($Ps_2$= 1.06$\times$$10^-7$ atm, ($Po_2$ = 3.11$\times$$10^-18$ atm) environment has been observed and analysed using XRD, SEM/EDS. To investigate the possibility of protective film formed on the surface of the alloys, Aluminium, Nickel were selected as alloying elements. Thermodynamic phase stability diagram was used to predict the reaction path of scale formed on Fe - Cr - X alloys. Parabolic rate constant($K_p$) value with 6wt% Al in Fe - 25Cr alloy decreased significantly compared with the Fe - 25Cr alloy without 6wt% Al. Since thin layer of defect free sulfide film, (Al, Cr)Sx, was formed at the alloy/scale interface. Fe - rich sulfide scale at outer layer and Cr - rich sulfide scale containing porosity at inner layer of Fe - 25Cr alloy have been observed. The reaction path for these scales could be predicted by the thermodynamic stability diagram.