The effect of H2S concentration and corrosion products coverage on electrochemical and hydrogen permeation behaviors of pipeline steel was studied by electrochemical methods. The corrosion behavior under different H2S concentration was investigated by immersion testing and weight loss method. The corrosion products were studied by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The results show that electrochemical and hydrogen permeation behaviors were mainly affected by the concentration of H2S molecules in the solution and adsorbed HS-. With the common influence of both the steady-state hydrogen permeation current density increased with the H2S concentration increases and then reached a stable value. The results of different H2S concentration tests showed that the corrosion product structure and density might influence the degree of hydrogen absorption and obstruction on hydrogen permeation behavior.