This study focuses on an advanced methodology for the quantitative assessment of fire risk, which is based on the analysis of the functionality and interaction of protective barriers aimed at enhancing the effectiveness of risk-oriented fire safety management. Scientific relevance of the topic stems from the pressing need to integrate a multi-level approach to fire safety management. This includes the application of probabilistic modeling techniques, consideration of time-dependent changes in the reliability of fire protection systems, and assessment of their degradation processes under prolonged operational conditions. The research employs a probabilistic-deterministic framework that combines quantitative risk estimation with the analysis of the interrelations among different categories of safety barriers and their collective impact on mitigating the consequences of fire incidents. The results indicate that the proposed methodology achieves a reduction in estimated fire risk values by 27–40%, primarily due to the inclusion of evolving technical conditions of protective systems and the improved accuracy of forecasting their performance under operational impacts. The conclusions highlight the necessity for further refinement of the methodology, including the integration of real-time monitoring data and the development of regulatory mechanisms to support its practical implementation.