Evaporation and micro-explosion of water-in-oil emulsion droplets composed of water and polycyclic aromatic hydrocarbons (PAHs) were characterized by molecular dynamics simulation at 300 to 600 °C and 0.2 to 1.5MPa. The driving force for micro-explosion of emulsion droplets comes from the difference between environment temperature and boiling point of water. Also, the evaporation potential of oil phase has a significant influence on the intensity of micro-explosion. An increase in water droplet diameter within a certain range, an increase in environment temperature and a decrease in environment pressure are beneficial to increasing the probability and intensity of micro-explosion. After an intense micro-explosion, the number of oil molecules in the resulting child clusters can be less than 20% of the initial number of oil molecules in the emulsion droplets. The time required for complete evaporation of emulsion droplets depends on the evaporation of the largest child cluster produced by micro-explosion.