Due to active actions of groundwater and geothermal, the stability of underground engineering is important during geological structure active area. The damage mechanical theory and statistical mesoscopic strength theory based on Weibull distribution are widely used to discuss constitutive behaviors of rocks. In these theories, a statistical method is used to capture mesoscopic properties of rocks in order to generate a realistic behavior at a macroscopic scale. Based on the above theories, this paper aims at establishing a constitutive relation of brittle rocks under thermal-mechanical coupling conditions. First, a statistical damage constitutive model was established by considering the thermal effects and crack initiation strength. Subsequently, the parameters of the model were determined and expressed according to the characteristics of stress-strain curve. Third, the model was verified by conventional triaxial experiments under thermal-mechanical actions, and the experimental data and theoretical results were compared and analyzed in the case study. Finally, the physical meaning of the parameters and their effects on the model performance were discussed.