In a number of studies, the formation of perovskite CaTiO3 (CTO) phase was observed at the interface layer when depositing hydroxyapatite coatings onto biomedical titanium alloys. Recently, CTO itself has been proposed as a suitable candidate for biocompatible coatings for medical implants, particularly Ti implants. We report on polycrystalline CaTiO3 coatings prepared on silicon and titanium using a sol-gel technique followed by rapid thermal processing (RTP). The structure, composition, and surface morphology of CTO coatings RTP crystallized in the range of 500-800 °C for 30-180 s were investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and non-contact optical profilometry. Crystallization of single-phase CTO coatings on titanium is observed starting at 500 °C, while on Si, the coating remains amorphous at 550 °C, and an intermediate CaCO3 phase is observed at up to 650 °C. © 2004 Elsevier B.V. All rights reserved.