Long-term steel reinforcement corrosion greatly impacts reinforced concrete structures, particularly in marine and coastal settings. Concrete failure leads to human casualties, requiring extensive demolition and maintenance, which represents an inefficient use of energy and resources. This study utilizes microscopic observation, atomic force microscopy (SKPM), electrochemical experiments, and XPS analysis to investigate the corrosion behavior of 500CE and 500E under identical conditions. We compared 500E with 500CE, supplemented with 0.94% Cr, 0.46% Mo, 0.37% Ni, and 0.51% Cu through alloying element regulation to obtain a finer ferrite grain and lower pearlitic content. The results indicate that 500CE maintains a stable potential, whereas 500E exhibits larger grain sizes and significant surface potential fluctuations, which may predispose it to corrosion. In addition, despite its more uniform microstructure and stable electrochemical activity, 500E shows inferior corrosion resistance under prolonged exposure. The electrochemical corrosion rate of 500CE in both the pristine and passivated states and for various passivation durations is slower than that of 500E, indicating superior corrosion performance. Notably, there is a significant increase in the corrosion rate of 500E after 144 h of exposure. This study provides valuable insights into the chloride corrosion phenomena of low-alloy corrosion-resistant steel reinforcement in service, potentially enhancing the longevity of reinforced concrete structures.