In Northern Chile, large amounts of highly corrosive solutions are currently generated in the process of cathode washing after completing the electrowinning or electrorefining process of copper. This study investigates the electrochemical behavior of ASTM A36 carbon steel in pregnant-leach-solution (PLS) wash water. Measurements of electrochemical impedance spectroscopy and linear sweep voltammetry, complemented with weight loss measurements, were performed. Four ratios of PLS containing reverse osmosis (RO) water are evaluated, considering both quiescent and rotating conditions of the steel specimen. The results indicate that oxygen reduction, hydrogen evolution, and iron oxidation reactions are all involved during the corrosion of carbon steel in pure RO water, with the corrosion rate increasing up to 4 times under rotating conditions. In the case of corrosion in RO wash water containing PLS, a galvanic process occurs whereby copper is reduced at the expense of iron oxidation, superimposed on former partial reactions. The deposited copper induces notable corrosion inhibition of steel, observed as a significant drop in corrosion rate from high initial to constant residual values. Morphological and X-ray analyses support that corrosion is affected by oxide layer formation and galvanic copper deposition, confirming the results obtained from electrochemical analysis and weight loss measurements.