This study explored the influence of Cl-ion and temperature variations on the corrosion behavior of pipeline steel in supercritical CO2 (s-CO2) saturated aqueous environments. The steel exposed to the s-CO2 saturated salt solution at 50°C shows a higher corrosion rate (CR) of 5.02 mm/year compared to that exposed to deionized (DI) water, which has a corrosion rate of 1.47 mm/year. This trend is more pronounced at higher temperatures. This performance enhancement is attributed to the formation of a dense and protective FeCO3 film, facilitated by the Cl-ion presence, with a more pronounced effect observed at higher temperatures. The corrosion mechanism, commencing with the impact of Cl- ions on interactions between CO2 and the dissolved HCO3- ions with iron at the steel surface, is comprehensively elucidated via density functional theory (DFT) in s-CO2 systems at varied temperatures. The findings from this study offer valuable insights into mitigating corrosion-related challenges in s-CO2 system.