By means of X-ray photoemission spectroscopy and low energy electron diffraction, we show that it is possible to grow good quality thin epitaxial CoO films on Fe(001) substrates, through deposition in oxygen atmosphere. In particular, the composition and the structure of CoO(001)/Fe(001) bilayer systems and Fe(001)/CoO(001)/Fe(001) trilayer systems have been investigated by monitoring the evolution of the chemical interactions at the interfaces as a function of CoO thickness and growth temperature. We observe the presence of Fe oxides at the CoO/Fe interface and of a thin layer of metallic cobalt at the upper Fe/CoO interface of trilayer systems. (C) 2008 Elsevier B.V. All rights reserved.