Novel oil-in-water (O/W) Pickering emulsions (PEs) were prepared using mesoporous nanosilica in combination with a pH-insensitive cationic surfactant as a stabilizer and show an interesting sensitivity to acids and bases. Adding a suitable amount of NaOH (nNaOH/ncationic surfactant ≥ 1) led to prompt demulsification within 10 s. Upon further adding HCl solutions (nHCl/nNaOH = 1), stable PEs re-formed after homogenization. These emulsions remained stable for over 30 days after 60 cycles, switching from stable to unstable and back to stable states, and showed a high salt tolerance. A mechanism for the switching of the Pickering emulsion (PE) to unstable and back to stable states was derived and involved anionic and neutral forms of hydroxyl groups at the mesopores of the mesoporous silica nanoparticles (MSNPs). This work reveals a switchable PE system involving a pH-insensitive surfactant, in which the species of oils and cationic surfactants can be arbitrarily selected, a feature that greatly expands the applicability of PEs.