The early formation of phosphate oxide formed on 316 stainless steel (316 SS), nickel-based Alloy 625, and titanium alloy TA8 exposed in supercritical water (400 °C, 25 MPa) containing phosphate, chloride, and oxygen was investigated. Phosphate corrosion products of austenitic stainless steel displayed the severest spallation. Stable phosphates oxide films were inclined to form on Alloy 625. TiO2 and Ti2O3 are the two main components of oxide films on TA8. There is a strong synergistic effect between phosphates, oxygen, and supercritical water, leading to severe corrosion. The corrosion behavior of the three alloys at the top and bottom of the reaction tube was compared. Both at the top of the reaction tube and at the bottom of the reaction tube, TA8 showed an increase in mass. 316 SS and alloy 625 showed mass gain at the top and mass loss at the bottom. The alloys’ detailed molten corrosion mechanism after exposure to supercritical water is discussed.