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Influence of temperature on the electrochemical and passivation behavior of 2507 super duplex stainless steel in the simulated desulfurized flue gas condensates in thermal power plant chimney are investigated. Cathodic reactions are enhanced with temperature, accompanying with the involvement of oxygen reduction when the temperature is raised to 60 °C or higher. The unchanged semiconductor type, enrichment of Cr and thickening of the passive film are observed as the temperature increases. The temperature-induced variations of film structure and doping concentrations are responsible for the degradation of protective ability of the passive film.