Despite many investigations on the corrosion behavior of NiTi shape memory alloys (SMAs) in various simulated physiological solutions by electrochemical measurements, few have reported detailed information on the corrosion products. In the present study, the structure and composition of the corrosion products on NiTi SMAs immersed in a 0.9% NaCl physiological solution are systematically investigated by scanning electron microscopy (SEM), x-ray energy dispersion spectroscopy (EDS), and x-ray photoelectron spectroscopy (XPS). It is found that attack by Cl− results in nickel being released into the solution and decrease in the local nickel concentration at the pitting sites. The remaining Ti reacts with dissolved oxygen from the solution to form titanium oxides. After long-term immersion, the corrosion product layer expands over the entire surface and XPS reveals that the layer is composed of TiO2, Ti2O3, and TiO with relatively depleted Ni. The growth rate of the corrosion product layer decreases with immersion time, and the corrosion product layer is believed to impede further corrosion and improve the biocompatibility of NiTi alloy in a physiological environment. It is found that the release rate of nickel is related to the surface structure of the corrosion product layer and immersion time. A corrosion mechanism is proposed to explain the observed results.