The sour resistant pressure vessel steel (ASTM A516) is required to develop for use as a heat exchanger cylinder and condenser in the petrochemical industry since the low quality crude oil containing a large amount of H2S gas is increasingly used. The pressure vessel steels with two different microstructures of ferrite/pearlite and bainite were tested in a sour environment. The microstructure affects significantly the formation of iron sulfide and dissolution rate of the steel. It is closely related with the size and distribution of the iron carbide (Fe3C) in the different microstructure of the steel since the iron carbide acts as the cathode to the steel matrix. In this study by using various electrochemical analytic tools such as potentiodynamic and potentiostatic polarization test the corrosion property of the steel was evaluated with respect to the microstructure of the steel matrix and sulfide formation kinetics. TEM was utilized for cross-sectional observation and GDS for identification of chemical composition as a function of depth. In addition the effect of various heat treatments of the tempering and simulated post weld heat treatment (PWHT) on the steel corrosion will be discussed in terms of change in the microstructure.