The corrosion behaviors of 316 stainless steel (316 SS), Inconel 600, Inconel 625, Hastelloy C-276 and TA10 coupons exposed in supercritical water (400 degrees C/25 MPa) with sodium chloride, sodium triphosphate and hydrogen peroxide were investigated by using SEM, XRD and XPS. 316 SS shows the most severe spallation of oxide scales and Inconel 600 exhibited the most severe pitting corrosion due to a lack of molybdenum in the alloy. TA10 showed the lowest corrosion rate and the slightest corrosion morphology. TA10 had corrosion rates less than 1.8 mmpy in the four experiments and a triplex oxide layer structure formed which consisted of TiO2/Ti2O3/TiO from outer to inner layer. The formation of (TiO)(2)P2O7 was observed on TA10 in oxidizing supercritical water containing phosphate. Phosphate shows significant corrosion inhibition for metal alloys in SCWO due to the formation of a passivating metal phosphate film. An oxide film growth mechanism, metal dissolution mechanism and metal salt precipitation mechanism are discussed in order to explain the corrosion behavior of the specimens in this research. (C) 2015 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.