Electrochemical measurements, x-ray photoelectron spectroscopy, and scanning tunneling microscopy have been used to study the effect of hydrogen peroxide on the passivity of titanium in a phosphate-buffered saline (PBS) solution. The results indicate that the passive film formed in the PBS solution--with and without addition of H2O2--may be described with a two-layer structure model. The inner layer has a structure close to TiO2 whereas the outer layer consists of hydroxylated compounds. The introduction of H2O2 in the PBS solution broadens the hydroxylate-rich region, probably due to the formation of a Ti(IV)-H2O2 complex. Furthermore, the presence of H2O2 results in enhanced dissolution of titanium and a rougher surface on a microscopic scale. Finally, a dark pigmentation (blue color) is observed when titanium has been exposed--for several weeks--to PBS with additions of H2O2.