To study the impact of the psychological and behavioral characteristics of people, fire environment, and evacuation routes on fire evacuation efficiency, this study focuses on a university library as the research subject. A fuzzy logic algorithm is employed to analyze how psychological and behavioral traits influence initial evacuation speed during a fire. Also, fire data simulated using PyroSim software is integrated, with gas temperature, CO concentration, and visibility quantified through empirical formulas to adjust the reduction factor of evacuation speed, examining the effects of fire-generated products on evacuation performance. By incorporating fire environment factors into the heuristic function and refining pheromone update rules through iterative strategies, the ant colony algorithm is enhanced to achieve path planning. Results show that the psychological–environmental-route correction method improves evacuation efficiency by 16.2% compared to traditional methods without correction. This demonstrates that the proposed correction method can improve the efficiency of building fire evacuation and provides theoretical support and technical solutions for future library fire safety management.