The protection of metal orthopedic implants against corrosion is a crucial medical problem. It was found that electrochemical polymerization of thin, passive poly(acrylic acid) (PAA) films on titanium and TiAlV substrates provides good anti-corrosion properties. In this work, an investigation of anti-corrosion features was carried out to clarify the hypothesis of the presence of an electrostatic contribution to the performance of a PAA coating. Ion release tests were performed at three different pHs; the pH dependence of the polymer swelling was examined by quartz crystal microbalance with dissipation monitoring, to establish the role of this phenomenon on the polymer barrier properties. The potential application of these PAA thin films as biocompatible protective coatings for metal implants and compatibility towards MG-63 human osteoblast-like cells was assessed.