Large-capacity toluene storage tank leakage accidents can lead to severe casualties and environmental damage. In this study, numerical simulation of the toluene leakage accidents is performed using PHAST and ALOHA softwares across 16 scenarios. The present research focuses on the dispersion of toluene lethal and toxicity clouds, as well as the associated risks from vapor cloud explosions and pool fires resulting from the large-capacity toluene storage tank leakage. Meanwhile, the effects of influential factors such as leakage height, wind speed, ambient temperature, and atmospheric stability on toluene leakage accidents are also discussed, and then the worst-case scenario of the toluene leakage accident is obtained. The effects of wind speed, ambient temperature, leakage height, and atmospheric stability on outcomes such as toxic clouds, vapor dispersion, explosions, and pool fires are also analyzed. The result reveals that toxic cloud dispersion increases with ambient temperature, while the impact of vapor cloud explosions and pool fires decreases with the increase of leak heights. Wind speed significantly affects pool fire spread. The influential factors related to maximizing hazard range including low leak heights, low wind speeds, high temperatures, and stable conditions are obtained. Risk analysis indicates that vapor cloud explosions significantly impact outdoor potential loss of life (PLLoutdoor) compared with other incidents. Scenario 4 within a directional range from 33.8 to 56.3° shows the highest incident frequencies, highlighting its importance for risk monitoring. These findings are crucial for enhancing emergency response strategies and safety protocols in industrial safety management.