Oxidation mechanism of Alloy 690 has been investigated in Pressurised Water Reactor (PWR) primary coolant conditions (325°C, aqueous hydrogenated media). Experiments performed with gold marker and RBS technique reveal that the passive film formation is the consequence of an anionic mechanism. This result is confirmed by experiments achieved with two sequences of corrosion in a H2 16O media and in a mixed H2 16O/ H2 18O media. The localisation of 18O by SIMS analysis in the thin passive layer underlines an oxidation mechanism due to oxygen diffusion by short circuits (like grain boundaries) in the oxide scale. Moreover grain boundary diffusion coefficient in chromite like oxide was estimated to be in the range 2 10-18 – 1 10-17 cm2.s-1 and compared to values extrapolated from higher temperature.