This paper studies the initial stages of iridescent tarnishes on titanium heat exchanger tubes in contact with running freshwater on the river Tagus in Spain for up to 20 months. Electrochemical impedance spectroscopy (EIS), scanning electron microscopy [(SEM with energy dispersive X-ray (EDX)] and X-ray photoelectron spectroscopy (XPS) in conjunction with argon-ion sputtering were the techniques used. The EIS data indicated a capacitive behavior, showing a semicircle that was better defined as the experimental time increased, indicating a decreasing tarnishing resistance of titanium. XPS and EDX results indicated that the main elements identified were calcium, phosphorus, nitrogen, and iron. The amount of these elements was higher on the tarnished titanium specimens than on the untarnished specimens. SEM analysis showed the presence of diatoms in the iridescent tarnishes on titanium tubes.