The thermal behaviors of high-temperature particle (HTP) and low-temperature particle (LTP) are investigated based on the bench-scale impinging entrained-flow coal-water slurry (CWS) gasification experimental platform with a modified visualization system. The size and velocity distribution of both particles, and the evolution of HTP are analyzed through the algorithmic and precise processing of the image sequences. In addition, in-situ temperature diagnosis of the particles during the reaction process were realized. The typical evolution process and the temperature of HTP in char oxidation stage are obtained. The results show that the concentration of HTP in the gasifier is greater than LTP, but the particle size is relatively small. Particles moving at the low speed (0–2 m/s) account for the largest proportion of both HTP and LTP. The char oxidation process lasts over 300 ms and can be divided into three reaction stages. During the reaction, the peak temperature at the center of the particle can reach more than 2000 K. The average temperature of the particles gradually increased, reaching a peak in reaction stage II (1500 K) followed by a gradual decrease. The particle temperature is affected by O/C and is prone to experience swelling and bubbling phenomena during char oxidation.