The long-term performance of the concrete–polymer cement mortar (PCM) interface under environmental exposure is crucial to the safety of the PCM overlaying method as the environmental exposure of the repaired structures caused further degradation of the interface, leading to a significant reduction in intended service life. This study investigates the durability enhancement effect of silica fume of the concrete–PCM interface, considering an individual action of elevated temperature (e.g., 60 °C) [constant (short and moderate duration) and cyclic conditions] and moisture content [continuous immersion and wetting/drying (W/D) cycle]. Our previous research confirmed that the use of silica fume forms more C-S-H with strong binding force and enhances the interfacial bonding strength due to the denser microstructure at the interface, and it is expected to be utilized for durability purposes under the aforementioned exposure conditions. Under all elevated temperature exposure conditions, the reduction percentage of the interfacial performance corresponding to the respective reference specimens reduced significantly with the inclusion of silica fume with overlay material. The occurrence of interface fracture at lower load and a greater number of pure interface fracture modes observed in normal PCM specimens compared to modified PCM specimens indicates a positive influence of higher adhesion with better durability of modified PCM overlay with substrate concrete. Under both conditions of moisture content, significant reduction in interfacial strength was observed in normal PCM specimens. In all cases, the reducing ratio of interfacial strength was higher in normal PCM compared to modified PCM, indicating a positive influence of silica fume under moisture content. Furthermore, silica fume inclusion shifts the fracture mode from pure interfacial fracture to composite fracture mode, indicating a positive response of silica fume to improve the resistance of interface fracture under moisture content. Conclusively, the use of silica fume improves concrete–overlay layer adhesion and enhances the bonding durability under environmental exposure.