The refractory materials required for waste-to-energy boilers endure severe working conditions, such as exposure to heat and hot oxidation / corrosion. Thanks to their high temperature properties cobalt-based alloys may respond to these properties requirements. In this work two model alloys based on cobalt and rich in chromium were elaborated by casting and samples were prepared by cutting and polishing. These samples were exposed, one to a hot complex gaseous mixture particularly aggressive reproducing the atmosphere in WtE boilers in service (presence of water vapor, di-oxygen, carbon di-oxide, hydrogen chloride), and the other to synthetic ashes, both for more than two hundreds hours. After test the samples were characterized by X-ray diffraction and SEM observations. On sample exposed to the complex gas stream a {10 to 15μm}-thick oxide scale formed on the surface of the sample exposed to the gas mixture. It involved all the elements of the alloy and it obviously developed both inwards and outwards as suggested by the position of the oxidized carbides.