The blister formation mechanism in electrogalvanized steel was studied by analyzing the blister’s internal structure. Electrochemical hydrogen charging was employed to absorb hydrogen into the steel plate and to induce blister formation. Analysis of the blister interior revealed that the initial formation of blisters occurred at the cracks located at the interface between the zinc layer and the steel substrate. These cracks originated from the steel substrate’s intergranular fracture or carbon contaminants’ adsorption on the steel surface. Grain boundary precipitates in hot-rolled plates form the intergranular crack after cold-rolling. A hydrogen anion was found inside the blister formed at the pre-existing intergranular crack. However, methylidyne (CH−) and methylene anion (CH2−) dissociated from methane, as well as hydrogen anions were detected inside the blister formed at the carbon-contaminated steel surface. Methane gas is generated by the combination of absorbed hydrogen with carbon inside the crack. This research clarifies the detailed formation mechanism of blisters in electrogalvanized steel.