Hydroxyapatite thin films were grown on layered structures by Pulsed Laser Deposition with the goal of investigating the interface of the ceramic film with the substrate. The latter consisted of Si/TiN/Ti sandwich structures. This multilayer substrate was also prepared by laser ablation earlier in the same experimental session. This particular type of structure was chosen in order to induce the in situ growth of hydroxyapatite directly onto freshly deposited Ti. We tried this way to avoid previous direct Ti exposure to air, hence its oxidation. The subsequent depositions of multilayers were performed with the aid of a carousel multi-target system mounted inside the irradiation chamber. This allowed for selecting in order the respective TiN, Ti and HA targets without opening the chamber between individual depositions. X-ray diffractometry, transmission electron microscopy and selected area electron diffractometry studies revealed the formation at the interface of a transition complex phase, 2 to 25 nm thick, consisting of a mixture of TiO2 and CaP phase. The specific growth of TiN and Ti phases was also investigated. (c) 2007 Elsevier B.V. All rights reserved.