The article undertakes the very important topic of the long-term durability of concrete in a natural draft concrete cooling tower with flue gas injection. The corrosive conditions, including temperature, relative humidity, and CO2 and SO2 gas concentrations, near the inner wall of a cooling tower with flue gas injection were monitored in real time to obtain the long-term durability performance of concrete. The pH and chemical compositions of the condensed liquid that adhered to the tower’s inner face and the macromorphology, compressive strength, and neutralization depth of in situ specimens were tested periodically. In addition, a finite element numerical simulation was conducted to simulate and verify the concentration distributions of CO2 and SO2 in the flue gas in the cooling tower. The results showed that the cleaned flue gas was enveloped, diluted, and uplifted by hot vapor in the cooling tower, and its concentration decreased. Meanwhile, the effective diffusion radius increased gradually as the flue gas rose. With the same elevation in the cooling tower, the concentration of flue gas decreased rapidly from the central point to the surrounding area. The air near the inner surface of the cooling tower was merely dampened air with a low concentration of acidic gas due to the gigantic diameter of the cooling tower. As a result, the injection of cleaned flue gas will not evidently increase the corrosion risk in a natural draft concrete cooling tower.