The mechanical properties and failure modes of concrete are controlled by its mesoscopic material composition and structure; therefore, it is necessary to study the deterioration characteristics of tunnel lining concrete under fire from a mesoscopic perspective. However, previous studies mostly analyzed the damage and failure process from a macro-homogeneous perspective, which has certain limitations. In this paper, a thermal–mechanical coupling test device was modified to simulate the state of concrete under tunnel fire conditions. Combined with CT technology, the macroscopic properties and mesoscopic characteristics of concrete were observed. Features were obtained, such as the change in compressive strength under fire, as well as mesoscopic deterioration characteristics. The damage variable D was defined to quantify mesoscopic damage, and the link between mesoscopic deterioration characteristics and macroscopic performance was established, which can be used to predict compressive strength loss through mesoscopic characteristics.