<p>Rock–concrete structures are commonly applied in practical engineering projects, and their mechanical properties and failure patterns are significantly affected by temperature and interface stress state. To investigate the influence of temperature on the bearing capacity and failure behavior of the rock–concrete interface, the bi-material disks were tested for Brazilian splitting with different loading angles at ambient temperature and high-temperature treatments. Loading angles change from 0° to 30°, and the stress state at which the interface was subjected ranged from tensile stress to tensile-shear stress to shear stress. The results show that high temperature will change the failure patterns of rock–concrete bi-material disks. At 25 °C and 100 °C, the failure patterns of the specimen are interface tensile fracture and combined fracture (interface shear fracture and matrix tensile fracture). At 300 °C and 500 °C, there are interface tensile fractures and interface shear fractures. At all loading angles, the peak load of specimens decreases with the increase in temperature, and the peak load decreases dramatically when the temperature increases to 300 °C. With the increase in loading angle, the tensile stress on the interface decreases, while the shear stress increases with increasing loading angle, and both decrease with the increase in temperature.</p>