In this study we examine the evolving state of electrolyte and corrosion processes associated with sodium chloride on copper at the initial stage of corrosion and the critical implications of this behavior on controlling kinetics and damage distributions. Sodium chloride droplets were placed on copper in humid conditions and the resulting electrolyte properties, corrosion products and damage were characterized over time using time-lapse imaging, micro Raman spectroscopy, TOF-SIMS and optical profilometry. Within minutes of NaCl droplet placement, NaOH-rich films resultant from oxygen reduction advanced stepwise from the droplets, leaving behind concentric trenching attack patterns suggestive of moving anode-cathode pairs at the alkaline film front. Corrosion attack under these spreading alkaline films was up to 10x greater than under the original NaCl drops. Furthermore, solid Cu₂Cl(OH)₃ shells formed over the surface of the NaCl drops within hours of exposure. Thermodynamic modeling along with immersed electrochemical experiments in simulated droplet and film electrolytes were used to rationalize this behavior and build a description of the rapidly evolving corroding system.