The stability of Pt/epitaxial Gd2 O3 /Si stacks is studied by monitoring the chemical and electrical properties following heat treatments in forming gas and in vacuum at temperatures between 400 and 650 °C. Our results show that stack instability is realized via diffusion of Gd through the Pt grain boundaries, which was observed after forming-gas annealing at 550 °C for 30 min. The Gd diffusion kinetics in forming gas is studied by secondary ion mass spectrometry analysis, showing that the diffusion process occurs according to C-type kinetics with an activation energy of 0.73±0.04 eV. Following vacuum heat treatments at 600 °C for 30 min, Si outdiffusion is observed, in addition to Gd outdiffusion. Si outdiffusion results in the formation of PtSi clusters on the metal surface following vacuum annealing at 650 °C. In contrast, in the case of forming-gas treatments, Si diffusion and silicide formation were detected only after annealing at 700 °C. The better stability of Pt/ Gd2 O3 /Si stacks in forming gas is correlated with the content of oxygen in the Pt layer during the treatment.