An austenitic stainless steel (TP 347H FG) was coated with a synthetic deposit and exposed, under laboratory conditions simulating straw-firing at 560 oC, for one week. Microscopic, diffraction and spectroscopic techniques were employed for cross-sectional and plan view ‘top-down’ microstructural characterization of the corrosion products. The corrosion products consisted of three layers: i) the outermost layer consisting of a mixed layer of K2SO4 and FexOy on a partly molten layer of the initial deposit, ii) the middle layer consists of spinel (FeCr2O4) and Fe2O3, and iii) the innermost layer is a sponge-like Ni3S2 containing layer. At the corrosion front, Cl-rich protrusions were observed. Results indicate that selective corrosion of Fe and Cr by Cl, active oxidation and sulphidation attack of Ni are possible corrosion mechanisms.