Using solely highly hydrophilic particles to stabilize emulsions, especially high internal phase emulsions, has always been an important challenge. Here pH-responsive Pickering emulsions stabilized by a low concentration of bare highly hydrophilic Ludox CL nanoparticles without surface modification or addition of surfactants are developed at neutral pH. The dispersed nanoparticles can be transformed into an aggregate state with a network-like structure near the isoelectric point, which contributes to the stabilization of the emulsions. Moreover, the vdW attraction between particles and droplets also plays a key role in the formation of emulsions, which can make the aggregated nanoparticles adsorb tightly around the droplets rather than penetrate the oil–water interface. The formed protective armor and network-like aggregates separate droplets from each other to prevent coalescence. At a low nanoparticle concentration (0.5 wt%), a high internal phase emulsion can be formed and can last up to half a year. This system can emulsify not only the hydrocarbon oil but also the fluoroalkane oil phase. Finally, organic–inorganic composite particles are fabricated using the template action of the Pickering emulsions. The method of preparing composite particles is more convenient than the traditional Pickering emulsion polymerization which often requires the modification of the surface of the hydrophilic particles or the addition of auxiliary monomers. This study provides a simple green strategy for the preparation of a more stable Pickering emulsion stabilized by surface-inactive nanoparticles and will broaden the scope of applications.