Si/SiO2 interfaces, an important functional part of silicon-based devices, are the structures most likely to cause failure. Under external load in the service state, Si/SiO2 interfaces can degrade in different forms, and they can change from an ideal symmetrical structure to an asymmetric structure with defects. To systematically analyze the Si/SiO2 interface, the research methods of microstructure, including characterization and modeling, are first introduced. Then, the effects of irradiation, high field stress, mechanical stress, and high temperature on Si/SiO2 interfaces are studied. Chemical bonds, conductive band structure, and interface roughness can be changed under high field and mechanical stress loads. In addition, defect initiation and impurity migration may occur due to irradiation and temperature loads, which can lead to the failure of devices. Under multiple types of loads, the degradation mechanisms are complex, and the interfaces become more sensitive, which makes investigations into interface degradation laws difficult. For improving the reliability of devices, a systematic analysis of the influence on Si/SiO2 interfaces under complex loads is summarized.