A novel electrostatic sensor array was designed to measure particle concentration downstream of a swirl burner. The fundamental mechanism and the primary constituent elements of the sensor array were described. The root-mean-square magnitude of the measured electrostatic voltage was determined as an indication of the particle concentration. The accuracy of the electrostatic sensor array was calibrated by the optical fluctuation method. Local particle concentrations at different cross-sections of the measuring chamber were measured to investigate the diffusion characteristic of the pulverized coal particles. Electrostatic sensor array showed its ability in the field measurement in this work. The measurements indicated that the velocity of the inner secondary air had a significant effect on the diffusion of the pulverized coal particles. The particles concentrated in the center of the cross-section after leaving the burner. With the development of the gas–solid two-phase flow, the particles distributed like a ring shape. The radius of the particle ring increased with the increase of the velocity of the inner secondary air. But the effect of the velocity of outer secondary air on the radius of the particle ring is very slight. The maximum radius occurred when the velocity of inner secondary air was 21 m/s, which was favorable for stable combustion.