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Chloride diffusion through concrete is influenced by harsh environmental conditions such as high ambient temperature and relative humidity. This paper examined the influence of temperature gradient on chloride diffusion in concrete under high ambient temperature conditions. Chloride diffusion tests using cylindrical concrete samples were performed in constant temperature and temperature gradient conditions. In a temperature gradient condition, a much higher chloride concentration was measured than at constant temperatures, which could not be explained only by the mass diffusion driven by the concentration gradient. A new analytical model of chloride diffusion with the mass diffusion term including the temperature effect and the thermo-diffusion term including the temperature gradient effect was applied to the results, which showed that the thermo-diffusion contribution was significant. Using the analytical model with the mass diffusion (DCl) and thermo-diffusion (DT) coefficients, the service life of reactor containment buildings (RCBs) in nuclear power plants (NPPs) in the Middle Eastern and North African (MENA) region was estimated. The results showed that the service life of the RCBs could be reduced by the temperature gradient, indicating the possible application of the proposed analytical model.