The thermal stability of bentonite is vitally important for its application in the casting field and the layer charge of montmorillonite (Qm) is one of its central crystal-chemical parameters. As the main component of bentonite, the influence of Qm on montmorillonite properties and behavior needs to be considered if bentonite is to be used in high-temperature environments. The objective of the current study was to investigate the relationship between Qm and the thermal stability of Chinese bentonite samples collected from Wuhu, Anhui Province (marked as WH); Xinyang, Henan Province (marked as XY); and Santai, Sichuan Province (marked as ST) below. The values of Qm were obtained using the O (11) method, and the structural properties of the bentonite samples were characterized by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), thermogravimetry-differential scanning calorimetry (TG-DSC), and field emission scanning electron microscopy (FESEM). The results showed that, in the samples investigated, Qm was inversely related to the thermal stability of bentonite. The Qm value (electrons per half unit cell, e/huc) was greatest for sample ST (0.725 e/huc), followed by sample XY (0.470 e/huc), and by sample WH (0.354 e/huc). The dehydroxylation temperature changed related to Qm; the sample with the largest Qm value was WH (701°C), followed by sample XY (684°C), and sample ST (630°C). After the samples were calcined at 600°C, sample WH had the best montmorillonite structural integrity with the greatest degree of reusability (78.21%); while the montmorillonite structures of samples XY and ST were destroyed, and their reusabilities were only 9.48 and 6.01%, respectively.