Silicon-substituted hydroxyapatites have been deposited onto Ti6Al4V substrates by sol-gel technology. The Ca(10)(PO(4))(6-x-y)(SiO(4))(x)(CO(3))(y)(OH)(2-x+y) coatings obtained, with silicon contents up to x=1 (2.8 wt.%), show a homogeneous and crack-free surface composed of particles smaller than 20 nm. The silicon enters into the apatite structure in the form of SiO(4)(4-) groups that partially substitute the PO(4)(3-) groups. The Si content and the Ca/P molar ratio of the coatings agree with those originally introduced in the sols. Layers with thicknesses around 600 nm show adhesion strengths superior to 20 MPa as determined by a pull-out test. The formation of an apatite layer onto these coatings after immersion in a simulated body fluid is enhanced by the presence of silicon.