Highlights MD simulations reveal CSH/SiO2 interface degradation under heat-water coupling. Thermal excitation enhances atomic mobility, disrupting Ca-O bond and H-bond networks. High temperature induces ITZ expansion and structural loosening of the interface. Water competes for active sites, turning direct CSH/SiO2 bonding into water-mediated. High temperature acts as a catalyst for deeper water molecule penetration into CSH.Abstract As the critical weak link in grouting reinforcement systems, the interfacial adhesion between cementitious grout and rock minerals is highly susceptible to performance degradation under high-temperature and water-rich conditions. In this paper, molecular dynamics simulations were performed across a temperature range of 293 K to 368 K to systematically investigate the effects of high-temperature and water-rich environments on the mechanical response, bonding structure, and dynamic behavior of the grout-rock interface. All simulations were performed using the LAMMPS package with the ClayFF force field. Two interface models, including a CSH/SiO2 direct-contact model and a CSH/H2O/SiO(2 )water-containing model, were constructed and subjected to uniaxial tensile tests. Key findings are as follows: (i) The tensile strength and interaction energy of the CSH/SiO2 interface exhibit distinct thermal degradation characteristics. The tensile strength decreases by 32.57%, and the interaction energy by 15.78% when the temperature rises from 293 K to 368 K. High temperatures induce expansion of the interface transition zone from 2.74 & Aring; to 4.60 & Aring; and loosening of the interface structure. (ii) High temperatures intensify atomic diffusion at the interface. The number and stability of Ca-O bonds and hydrogen bonds formed between CSH and SiO2 are reduced, leading to a decline in interfacial adhesion. (iii) The presence of an interfacial water layer significantly impairs the tensile strength and interaction energy of the interface. Compared with the direct-contact interface, the interaction energy is reduced by 38% at 293 K, and the tensile strength decreases by 73.58%. Water molecules in the solution compete for bonding sites of hydrogen bonds and Ca-O bonds at the interface, weakening the direct interaction between CSH and SiO2 and transforming it into an indirect interaction mediated by water molecules.