The corrosion of metals and alloys is a fundamental issue in modern society. Understanding the mechanisms that cause and prevent corrosion is integral to saving millions of dollars each year and to ensure the safe use of infrastructure subject to the hazardous degrading effects of corrosion. Despite this, corrosion detection techniques have lacked precise, quantitative information, with industries taking a top-down, macroscale approach to analyzing corrosion with tests that span months to years and yield qualitative information. Fluorescence, a well-established optical method, can fill the niche of early-stage, quantitative corrosion detection and can be employed for both bulk and localized testing over time. The latter, fluorescence microscopy, can be pushed to greater levels of detail with single-molecule microscopy, achieving nanometer spatial and subsecond temporal resolutions of corrosion that allow for the extraction of dynamic information and kinetics. This review will present how fluorescence microscopy can provide researchers with a molecular view into the chemical mechanisms of corrosion at interfaces and allow for faster, quantitative studies of how to detect and prevent corrosion.