Improper thermal cycles on duplex stainless steels can lead to the formation of detrimental phases or alter the proportion of ferrite and austenite phases, thus influencing the material’s mechanical properties and corrosion resistance. Therefore, this study aimed to evaluate the effect of aging (at 850 and 950 °C) and solubilization (at 1000 and 1150 °C) thermal treatments on microstructure, indentation hardness, elasticity modulus, and susceptibility to intergranular corrosion of UNS S32205 duplex stainless steel. The sigma phase (σ) formation in the aged samples, with hardness values between 8 and 10 GPa, was confirmed. Furthermore, the pieces treated from 1000 °C upwards showed that increased temperature favored the formation of more equiaxial grains and the ferrite fraction growth. The thermal treatments barely affected the elasticity modulus of austenite and ferrite grains, increasing the hardness of ferrite. The effect of sulfuric acid concentration in the intergranular corrosion was evaluated. Also, the deconvolution of the corrosion curves permits the determination of the influence of the different phases in the corrosion performance. These tests revealed sensitization only at the σ phase grain boundaries in the samples treated at 850 °C in electrolytes containing H2SO4 2.5 mol/L and HCl 1 mol/L. Although the treatment at 950 °C led to the σ phase formation, its higher corrosion resistance was ascribed to the lower volumetric fraction of this phase, its morphology, and its increased Cr mobility compared to the 850 °C treatment. Therefore, it was shown that the σ characteristics and the sulfuric acid concentrations are determining factors in the UNS S32205 intergranular corrosion resistance.