The electrochemical behavior of commercially pure titanium (CP Ti) and Ti-6Al-4V (Grade 5) alloy in phosphate buffered saline solution (PBS, pH = 7.4) at 37 °C (i.e., in simulated physiological solution in the human body) was examined using open circuit potential measurements, linear and potentiodynamic polarization and electrochemical impedance spectroscopy methods. After the impedance measurements and after potentiodynamic polarization measurements, the surface of the samples was investigated by scanning electron microscopy, while the elemental composition of oxide film on the surface of each sample was determined by EDS analysis. The electrochemical and corrosion behavior of CP Ti and Ti-6Al-4V alloys is due to forming a two-layer model of surface oxide film, consisting of a thin barrier-type inner layer and a porous outer layer. The inner barrier layer mainly prevents corrosion of CP Ti and Ti-6Al-4V alloy, whose thickness and resistance increase sharply in the first few days of exposure to PBS solution. With longer exposure times to the PBS solution, the structure of the barrier layer subsequently settles, and its resistance increases further. Compared to Ti-6Al-4V alloy, CP Ti shows greater corrosion stability.