Corrosion behavior of Fe–3 at.% Si alloy in 0.01 mol dm −3 HCl solution was investigated by using scanning electrochemical microscopy (SECM) as well as general electrochemistry. The rate of corrosion coupled with hydrogen evolution was initially 0.44 A m −2 but decreased significantly with time. Localized hydrogen evolution on the specimen surface was probed by an SECM system in which a force sensor was mounted to determine the probe height from the specimen surface. SECM images revealed that hydrogen evolution took place heterogeneously on the specimen surface depending on crystallographic orientation of substrate single grains in the initial stage and then became relatively homogeneous. Finally, a heterogeneous hydrogen distribution corresponding to the appearance of localized corrosion sites was observed.