Calcium phosphate (CaP) coatings on Ti6A14V substrate were elaborated by electrodeposition at different current densities (2, 5 and 10 mA/cm(2)). The surface morphology and the chemical composition of the coatings were characterized by scanning electron microscopy associated to X-ray microanalysis (SEM-EDXS). However, these CaP coatings are irregular specimens (rough surface, porosity, variable thickness), so the SEM-EDXS analysis becomes limited. Therefore, we carried out an experimental procedure to minimize these effects which is based on global analysis by SEM-EDXS confirmed by a nanometer scale analysis using scanning transmission electron microscopy associated to X-ray microanalysis. Moreover, phase analysis was performed by X-ray diffraction in order to corroborate the chemical characterization and to identify the different calcium phosphate phases as a function of current density. The results showed that at 2 mA/cm(2) current density, the coating is composed of an octacalcium phosphate: Ca8H2(PO4)(6) and its amorphous phase called OCPam. At 5 mA/cm(2), the coating is a mix of calcium deficient hydroxyapatite (Ca-def HAP): 2 Ca10-x(HPO4)(x)(PO4)(6-x)(OH)(2) with 0 < x <= 2 and its amorphous phase called Ca-def HAPam. And, at 10 mA/cm(2), the coating is mainly composed of an amorphous phase of Ca-def HAPam. Furthermore, cathodic reaction mechanisms of electrolytic CaP coatings on Ti6A14V are proposed to explain the different kinds of calcium phosphate obtained. (c) 2005 Elsevier B.V All rights reserved.