The effect of tempering temperature on the microstructure and intergranular corrosion property of 2205 duplex stainless steel (DSS2205) was determined using a boiling acid intergranular corrosion test (boiling 65% nitric acid and 50% sulfuric acid–ferric sulfate), an optical microscope, a transmission electron microscope, and a double-loop electrochemical potentiokinetic reactivation (DL-EPR) test. The results show that the ferrite content of the DSS2205 is about 50% in a specimen close to a solid solution state (1050 °C for 1 h, then water-quenched) when tempered at 675 °C–725 °C for 1 h. As the tempering temperature rises to 750 °C–800 °C for 1 h, the ferrite content drops gradually from 49% to 35%. M23C6, FeCr (σ phase), and Cr2N phases are precipitated when the specimen is tempered at 675°C–800 °C for 1 h. When the tempering temperature rises to 750 °C–800 °C for 1 h, the content and size of σ phase increase significantly. In the boiling acid intergranular corrosion test, when the specimen is tempered at 675 °C–725 °C for 1 h, the corrosion rate is higher than when it is tempered at 750 °C–800 °C for 1 h. In the DL-EPR test, when the specimen is tempered at 675 °C–800 °C for 1 h, the intergranular corrosion sensitivity rises gradually. External polarization is added during the DL-EPR test, and the test principle is different from that of the boiling acid intergranular corrosion test, resulting in a different sensitivity to intergranular corrosion compared to boiling acid intergranular corrosion.