Conventional gravitational wet scrubbers, which generally perform removal of fine particles with low efficiency, cannot meet new standards for pollution emissions. One way of improving the collection efficiency of fine particles is to impose additional electrostatic forces upon particles by means of particle-charging, or droplet-charging, or even opposite-charging of particles and droplets. A Monte Carlo method for population balance modeling is presented to describe the particle removal processes of gravitational wet scrubbers with electrostatic enhancement, in such a way that the grade collection efficiency and particle size distribution are calculated quantitatively. Numerical results show that, the grade collection efficiency of submicron particles is only ca. 5 % in conventional wet scrubbers. However, it reaches ca. 25 % in particle-charging wet scrubbers, ca. 70 % in droplet-charging wet scrubbers, and even above 99 % in opposite-charging wet scrubbers. Furthermore, population balance modeling is used to optimize the operational parameters of the droplet-charging wet scrubbers by means of the quantitative comparison of the grade collection efficiency. It is found that the operational parameters that are beneficial to the high-efficiency removal of fine particles are faster gas velocity, slower droplet velocity, larger liquid-to-gas flow ratio, larger charge-to-mass ratio of droplets, smaller geometric mean diameter and smaller geometric standard deviation of droplets.