Scanning electron microscopy (SEM) micro-morphology analysis, X-ray diffraction (XRD) and energy-dispersive X-ray diffraction (EDX) component analysis were conducted on the fouling of continuous emission monitoring system (CEMS) sampling tube at the outlet of limestone-gypsum wet flue gas desulfurization (WFGD) of unit 1 in a 600 MW supercritical coal-fired power plant in Inner Mongolia Autonomous Region. The results show that the main component of fouling was ammonium dihydrogen phosphate, which was generated by the reaction between phosphoric acid in the phosphoric acid titration device and the NH3 escaping from the selective catalyst reduction (SCR) denitrification system, and corresponding treatment measures were taken. It indicates that the average value of ammonia escape was reduced from 1.79 ppm to 1.54 ppm through the ammonia injection optimization test of the SCR denitrification system (at the load of 410 MW of the unit), which effectively reduced the generation of fouling. This research provides reference for improving the reliability of coal-fired unit operation after ultra-low emission transformation.