The online measurement of coal ash has overcome the shortcomings of chemical tests. However, there could be large fluctuations and errors in the results of online ash monitors because of the transient change in coal quality resulting from different geological conditions in the mining process. In this study, to resolve the problems of the dual-energy γ-ray online ash monitor in the Linhuan Coal Preparation Plant, we investigated the internal factors, such as the composition of multimineral and multicoal, and external factors, such as the moisture and impurities, which affect the measurement results of the coal ash monitor. Furthermore, we developed a mathematical model to determine the effect of relevant factors on the coefficient of the online ash monitor, which revealed the relationship between coal composition and the parameters of the ash monitor, ensuring the stable and accurate measurement of ash in clean coal. The method of determining parameters used in the case of coal blending has been applied in the Linhuan Coal Preparation Plant. By comparing with tested ash content, the average absolute error and relative error for daily ash content measured in April are 0.21 and 2.18%, respectively. Meanwhile, it shows certain accuracy and reproducibility while opposed to the daily average absolute error of 0.22 and relative error of 2.39% in May.