The steel-concrete interface determines the steel corrosion and the durability of concrete structures. In this paper, the relationship between macropores and localized corrosion is quantified, based on the natural deterioration of 5 wt% Cr steel reinforced mortar and laboratory tests of 5 wt% Cr steel in the saturated calcium hydroxide solution. The results show that, considering environmental factors with the same chloride content and water saturation, large interfacial macropores are always the weakest zones at which both corrosion initiation and propagation preferentially take place. The localized rate of steel corrosion (mm/year) increases linearly with the logarithm of the macropore volume (μL), and the slopes are in the range of 0.05–0.11 depending on the chloride level. The weakened pH buffering effect of solid Ca(OH)2 at interfacial macropores is not the only reason for this phenomenon; the impacts of macropores and their volume on the electrochemical corrosion process are also significant. In small macropores, both cathodic and anodic polarizations are strengthened, and the thermodynamic driving force of the iron dissolution reaction is reduced.