In recent years, much more emphasis than before has been placed on fire safety regulations by the local and central authorities of China, which makes fire risk assessments more important. In this paper we propose a new fire risk assessment approach for large-scale commercial and high-rise buildings that aims to evaluate the performances of their fire safety systems; this should improve the fire risk management and public safety in those buildings. According to the features of large-scale commercial and high-rise buildings, a fire-risk indexing system was built, and based on it we established a scientific fire risk evaluation system. To this end, the fuzzy analytic hierarchy process (FAHP) was used to assign a reasonable weight to each fire risk factor in the evaluation system. In addition, we revised the original scores by analyzing the coupling relationships among the fire risk factors. To validate our system, we selected 11 buildings in Shandong province and collected their fire safety data. Then, we calculated the final scores for the fire safety management of those buildings, and the results show that: (1) our fire risk evaluation system can assign reasonable weights; (2) the proposed evaluation system is comprehensive and has strong interpretability, since it exploits the coupling relationships among the risk factors. The novelty of the proposed approach lies in that it integrates opinions from multiple experts and utilizes coupling relationships among the factors. Further, the feedback from the approach can find not only the weaknesses in fire risk management, but also the potential causes of fires. As a result, the feedback from our assessment can assist the safety chiefs and inspectors with improving fire risk management.