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To address the problems of poor measurement accuracy and long service life of SO2 electrochemical gas sensors when used in thermal power plant areas, fly ash emitted from a thermal power plant in China was used as the research object. Based on the analysis of the morphological characteristics of fly ash particles, theoretical calculations were used to obtain the settling speed of fly ash particles and the amount of fly ash deposited at different times, and then the impact of fly ash on the measurement error of a SO2 electrochemical gas sensor was investigated by experimental tests. The research results show that the particle size distribution of fly ash is 2–11 μm, the average settling speed of fly ash particles is 1.34 × 10−3 m/s, and the deposition amount of fly ash on the surface of the sensor inlet film is 0.95 mg per day. The deposition time of fly ash affects the sensor measurement error, and the longer the deposition time, the larger the sensor measurement error, which is due to the reduction of gas diffusion area S and diffusion coefficient K in the sensor caused by fly ash deposition. Fly ash deposition has a greater impact on the sensor when measuring low concentration gases. The higher the gas concentration, the lower the measurement error, because the higher the gas concentration, the faster the gas reaches the working electrode area and the higher the effective SO2 concentration detected in the limited response time. When using SO2 electrochemical sensors in environments with high concentrations of fly ash or dust, it is recommended to install dust-proof devices (such as air-permeable filter membranes with a pore size of less than 4 μm) and regularly clean the deposited fly ash, which can improve the accuracy of the sensor measurement and extend the service life. [ABSTRACT FROM AUTHOR]