This work reports the effects of microstructural changes due to the secondary phases, in particular sigma (σ), on the mechanical properties and electrochemical behavior of thermally aged duplex stainless steel (DSS). Structural, morphological, mechanical, and electrochemical characterizations were performed. Sigma phase content increased with increasing aging treatment time. It had a net-like shape, as observed by electron backscatter diffractometry (EBSD). Its presence directly damaged mechanical properties. The corrosion assessment included electrochemical impedance spectroscopy (EIS) in 1 M NaCl solution at temperatures of 25, 40, and 65 °C. EIS results demonstrate that an increase in the σ phase content decreased the corrosion resistance (21.1–0.8, 3.5–0.3, and 3.1–0.2 kΩ cm² at 25, 40, and 60 °C, respectively).