AbstractWith the development and utilization of high‐sulfur coal, generating ammonium bisulfate (ABS) and ammonium sulfate (AS) during the coal combustion process has garnered increasing attention. This study examined the formation of ABS and AS under varying temperatures and different initial reactant ratios of SO3 and NH3 by establishing a self‐constructed experimental setup. Based on the experimental data, the equilibrium constant change diagram for the ternary reactions leading to ABS and AS formation was derived. The initial temperatures for forming gaseous ABS and AS were estimated to be approximately 416.33°C and 393.56°C, respectively. Consequently, this study fills the data gap of the equilibrium constant of gaseous ABS formed at high temperatures and furnishes the selective catalytic reduction (SCR) system with quantifiable and notably expedient means of technical analysis.