The corrosion behavior and mechanism of hot-dip galvanized steel and interstitial-free (IF) substrate with alkaline mud adhesion were investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD), electrochemical impedance spectroscopy (EIS), and linear polarization. The results show that non-uniform corrosion occurs on the galvanized steel and IF substrate during 250 h with the mud adhesion. The corrosion products on the galvanized steel are very loose and porous, which are mainly ZnO, Zn₅(OH)₈C₁₂·H₂O and Zn(OH)₂, and Fe-Zn alloy layer with a lower corrosion rate is exposed on the galvanized steel surface; however, the corrosion products on IF substrate are considerably harder and denser, whose compositions of rust are mainly FeOOH and Fe₃O₄, and several pits appear on their surface. The results of continuous EIS and linear polarization measurements exhibit a corrosion mechanism, that is, under activation control, the charge transfer resistances present different tendencies between the galvanized steel and IF substrate; in addition, the evolution of linear polarization resistances is similar to that of charge transfer resistances. The higher contents of dissolved oxygen and Cl^- ions in the mud play an important role in accelerating the corrosion.