The oxidation behaviour of P91 steel with and without Al-CVD-FBR coating was investigated by means of mass spectrometry and TG measurements. All samples were oxidized at 650°C for 190 h in an atmosphere of Ar ? 40%H 2 O. TG-MS experiments were conducted in a closed steam loop in order to obtain information about the oxyhydroxides formation as reaction between coatings and steam. During the oxidation of Al-CVD-FBR/P91 sample were detected volatile species as, FeO(g), Al 2 O 2 (g) around 25 h of test. AlOOH(g) and FeOOH(g) species around 100 h. FeOOH(g), Fe(OH) 3 (g) species around 125 h. FeOOH(g), Fe 2 O 3-H 2 O(g) species around 150 h. CrO 2 (g), volatile species around 175 h. Finally, Al(OH) 2 (g), Al(OH) 3 (g), Fe(OH) 3 (g) volatile species around 190 h. From those results the role of the coating element could be established and optimized for the coating durability. The morphology/composition and structure of oxidized samples were also studied using the SEM-back scattered electron images/EDS and XRD techniques.