Interdiffusion at interfaces between several materials in integrated structures is becoming more and more challenging. We performed a deep study of diffusion in BaTiO3/Si films using X-Ray Diffraction analysis, Rutherford Backscattering Spectrometry and X-ray Photoelectron Spectroscopy at intermediate annealing stages. We show that controlling local chemistry through inter-diffusion phenomena at interfaces is possible thanks to the structural and chemical matching between BaTiO3 and fresnoite. BaTiO3/Si stacks can serve as a model system to investigate the interphase generation at interfaces. (C) 2011 Elsevier B.V. All rights reserved.