Additive-swollen PNIPAM-based microgels exhibited enhanced hydrophobicity and superior emulsifying capability, which spontaneously assembled and jammed at oil–water interfaces, resulting in a significant interfacial energy decrease. The additive-swollen microgels formed a tightly packed, elastic, and responsive microgel monolayer. The feasibility of the strategy was verified by preparing various inverse W/O Pickering emulsions and high internal phase Pickering emulsions (HIPPEs). More importantly, this straightforward formation strategy of microgel-stabilized inverse W/O Pickering emulsions offered a novel platform to create functional materials with customized inner structures from microscale (e.g., responsive core–shell hydrogel microspheres and colloidosomes) to macroscale (e.g., hierarchical porous materials) that can be used for potential applications, such as recyclable contaminant removal and droplet manipulation.

The results show that UV irradiation alone cannot induce emulsion instability. However, when PAG is added to the oil phase, the Pickering emulsions exhibit a significant decrease in pH under UV irradiation, ultimately leading to emulsion destabilization and phase separation. At a UV intensity of 20 mW/cm2 for 2 min, the H+ release from the PAG significantly lower the emulsion’s pH, causing the SiO2-PDMAEMA particles to detach from the oil–water interface and resulting in emulsion instability. Higher concentrations of SiO2-PDMAEMA particles in the emulsion require more PAG to induce instability, as confirm by confocal laser scanning microscopy (CLSM) image. This study presents a versatile approach to develop photo-responsive Pickering emulsions which can have potential applications in areas such as drug delivery, cosmetics, and responsive materials.