With progressive urbanization and the development and utilization of urban underground space, underground urban complexes (UUCs) have been increasingly used. UUCs have brought much convenience to people’s lives. However, due to their enclosed nature and complexity, it has been an urgent issue to avoid (or reduce) casualties and allow rapid and safe evacuation of people during an emergency. In this study, the evacuation simulation software Pathfinder was used. Based on the steering model, the variation of the total evacuation time and pedestrian flow at main exits with different simulated evacuation measures, congestion at key nodes and people’s path selection were compared and analyzed. Then, the critical locations in the spatial layout of UUCs that were prone to evacuation bottleneck effects were focused on and determined. The evacuation effectiveness of UUCs in an emergency was studied to investigate the problems of emergency evacuation in UUCs. It is found that in UUCs, the bottleneck effects were likely to occur at stairway entrances and exits as well as supermarket checkout counters and caused severe congestion. These locations should be focused on during emergency evacuation. For key locations prone to evacuation bottlenecks, increasing the width of exits or setting up auxiliary evacuation channels could be an effective measure to improve evacuation efficiency. In addition, formulating rational evacuation rules can be a favorable measure for emergency evacuation. However, during the evacuation, the herd mentality in people has an uncertain (positive or negative) impact on evacuation effectiveness. Setting up diversion walls may improve evacuation efficiency and reduce congestion to a certain extent, while evacuation confusion and chaos are prone to occur after diversion. These findings in this study have significant implications for improving the emergency management of UUCs.