Herein, the chloride-induced stress corrosion cracking (SCC) mechanisms of UNS S32205 duplex stainless steel (DSS) reinforcing bars in alkaline and carbonated solutions are studied. Electrochemical monitoring and mechanical properties were tested using linear polarization resistance and electrochemical impedance spectroscopy, coupled with the slow strain rate tensile test (SSRT) to evaluate the SCC behavior and unravel the pit-to-crack mechanisms. Pit initiation and crack morphology were identified by fractographic analysis, which revealed the transgranular (TG) SCC mechanism. HCO3− acidification enhanced the anodic dissolution kinetics, thus promoting a premature pit-to-crack transition, seen by the decrease in the maximum phase angle in the Bode plot at low frequencies (≈ 1 Hz) for the carbonated solution. The crack propagation rate for the carbonated solution increased by over 100% compared to the alkaline solution, coinciding with the lower phase angle from the Bode plots, as well as with the lower charge transfer resistance. Pit initiation was found at the TiN nonmetallic inclusion inside the ferrite phase cleavage facet, which developed TG-SCC.