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The present work studies the effect of fly ash content (0–25 wt.%), pH (8, 12.5), and steel type (316L, 304L) on the cyclic polarization of stainless steel rebars in electrolytes, simulating fresh concrete exposed to acid rain and corroded concrete cover that has exposed the reinforcement to direct acid rain attack. At the same time, it tries to elucidate the corrosion inhibition activities of a Greek lignite fly ash that is a high-Ca fly ash with a questionable effect on the corrosion resistance of concrete. A higher pH results in lower corrosion rates for both steels and all fly ash content. However, different passivity trends are noted for the two steels as a function of pH. The partial replacement of Ca(OH)2 with fly ash up to 20 wt.% has a beneficial effect on the electrochemical behavior of the stainless steel rebars, in terms of both uniform and localized corrosion resistance. However, this trend is reversed at 25 wt.% FA. The reasons for such trends are explored via microstructural examinations of the steels after polarization and XRD analysis of fly ash, as well as reinforced concrete containing fly ash.