We investigate by different complementary methods the processes occurring when a polydimethylsiloxane film is used as interlayer for a silver doped hydroxyapatite coating. The X-ray diffraction and Fourier Transform Infrared Spectroscopy measurements show that the hydroxyapatite doped with silver is in a crystalline form and someSiO44-ions formation takes place at the surface and in the bulk of the new hydroxyapatite doped with silver/polydimethylsiloxane composite layer. The possibility ofSiO44-ions incorporation in the structure of silver doped hydroxyapatite by the mechanism ofSiO44-/PO43-ions substitution is analysed. The new formed silver doped hydroxyapatite/polydimethylsiloxane composite layer is compact, homogeneous, with no cracks as it was shown by Scanning Electron Microscopy and Glow Discharge Optical Emission Spectrometry.