In this paper, montmorillonite inhibitors modified with polyhydroxy functional groups by gluconic acid (GA) were successfully prepared. The particle size distribution, composition, surface functional groups, and pyrolysis characteristics of the pure montmorillonite powders (Mt) and the gluconic acid modified powders (G-Mt) were analyzed by using a laser particle analyzer, X-ray diffraction (XRD), Fourier transform infrared (FTIR) and thermogravimetry–differential scanning calorimetry (TG-DSC), respectively. The suppression effect of Mt and G-Mt on the 9.5% methane–air premixed gas was tested in a 20 L spherical explosion device and a 5 L pipeline experimental system. The results show that G-Mt displays a much better suppression property than that of Mt. The optimal explosion suppression effect concentration of Mt or G-Mt powders is about 0.25 g·L⁻¹. In this concentration, for G-Mt, the maximum explosion pressure declined by 26.7%, the maximum rate of pressure rise declined by 74.63%, and the time for the flame front to reach the top of the pipe was delayed by 242.5%. On the basis of the experimental data, the better suppression effect of G-Mt than Mt might be attributed to the presence of more hydroxyl groups on the surface.