The ingress of oxygen into pressure vessels used in oil & gas production and transportation could easily result in serious corrosion. In this work, the corrosion behaviors of Q345R steel at the initial stage in 1 wt.% NaCl solution were investigated using electrochemical techniques. The effects of oxygen concentration, temperature and pH on corrosion behaviors were discussed. Simultaneously, a numerical model based on the mixed potential theory was proposed. The results show that the proposed model accords well with the experimental data in the pH range from 9.0 to 5.0. In this pH range, the oxygen reduction reaction, H⁺ reduction, water reduction, and iron oxidation can be quantitatively analyzed using this model. However, this model shows a disagreement with the experimental data at lower pH. This can be attributed to the fact that actual area of reaction on the electrode is much smaller than the preset area due to the block effect resulted from hydrogen bubbles adsorbed on the electrode surface.