A type of coal with low calorific value and high ash content, locally known as mediocre ash coal (MAC), has been discovered in the interlayer of stratified coals in Jiang Jun Temple area Zhundong district, Xinjiang, China. In order to investigate slag deposition on the convective heating surface during co-combustion of MAC and Wucaiwan Ca-rich Zhundong Coal (WCW), a 0.4 MW pilot-scale facility, with tube panels #1 and #2 located in horizontal flue gas ducts, was constructed. The tube panels were designed to simulate the superheater and reheater of the Π-type boiler. FactSage was utilized to simulate the material balance, whereas the classic models were employed to calculate the slag viscosity. Combustion tests were conducted while maintaining flue gas temperatures (FGT) of 1050∼1100 °C and 900∼950 °C at tube panels #1 and #2, respectively, which were consistent with those observed during sole combustion of WCW. The slags collected from tube panels were analyzed by X-ray fluorescence, X-ray diffraction and Scanning Electron Microscopy coupled with Energy Dispersive X-ray Detector. Furthermore, Computer-Controlled Scanning Electron Microscopy analysis was used to obtain a quantitative characterization of the symbiotic relationship among mineral elements. The study of co-combustion MAC led to the following conclusions: The liquid phase ratio of slag decreased by 44% compared to sole combustion of WCW at 1100 °C. The viscosity was higher than that of sole combustion of WCW from 900 to 1650 °C. Compared to the sole combustion of WCW, the average S, Ca, and Na contents in the slag obtained on the two tube panels decreased by more than 85%, 40%, and 43.5% respectively. Sulfate formation in the slag on the tube panel was significantly reduced at medium to low FGT, and no Na2SO4 and CaSO4 compounds could be detected in the slag. The interaction between Fe-bearing minerals and Si- and Al-bearing minerals during combustion was evidently stronger than that between Ca-bearing minerals and Si- and Al-bearing minerals during combustion. The interaction of Fe with Ca/Na during medium to high FGTs led to a decrease in Si/ Al consumption, thereby increasing their availability for reacting with Ca/Na at medium to low FGTs. As a result, the formation of Na2SO4 and CaSO4 was inhibited.