The work reported herein deals with the interaction among the thermally sprayed coatings and steel substrate in acid aqueous solutions investigated by using the electrochemical process. Thermally sprayed coatings on steel substrate for such as the tribological applications except for the sacrificial anode property have been extended. The environment of these machinery components is often utilized accompanied with the aqueous solutions. The galvanic corrosion occurred in aqueous solutions among the metals or alloys have been well known. In the actual spray process, the formation of penetrated pores or crevice defects are not generally avoided. In the aqueous solution environment, the penetrated defects cause the galvanic corrosion between coating and steel substrate, and tend to be occurred the coating spalling. In this work, the electrochemical process was employed to determine the corrosion phenomena. The preferable combination of sprayed coatings and steel substrate are discussed and the examples of design of the intermediate layers are proposed.