A localized electrochemical impedance spectroscopy (LEIS) technique was used to characterize in situ the micro-electrochemical activity of inclusions contained in an American Petroleum Institute (API) X100 steel in a near-neutral pH solution. It is found that there exists an electrochemical heterogeneity between inclusions and the adjacent steel matrix. Consequently, a galvanic couple is formed to result in the locally preferential dissolution. The local electrochemical activity of the inclusion depends on its composition. A Si-enriched inclusion is associated with a high electrochemical activity, and the preferential dissolution of the inclusion generates a local microvoid, whose further dissolution initiates a corrosion pit. An aluminum oxide-enriched inclusion is more stable than the adjacent steel matrix. The preferential dissolution would occur on the steel, causing the “drop-off” of the inclusion and generating a corrosion pit.