The evolution of rust on MnCuP weathering steel submitted to a simulated coastal atmosphere was investigated by corrosion weight gain, scanning electron microscopy, X-ray diffraction, and electrochemical methods. The results indicate that the higher corrosion rate during the first stage than that during the second stage is related closely to the rust composition and electrochemical properties. The corrosion rate evolution is caused by the formation of a protective rust layer with a higher relative amount of α-FeOOH. The rust initially enhances and then stabilizes the cathodic process, but the anodic process tends to be inhibited by the protective rust layer.