Pickering emulsions (PEs) are stabilized by particles at the water/oil interface and exhibit superior long-term stability compared to emulsions with molecular surfactants. Among colloidal stabilizers, nano/microgels facilitate emulsification and can introduce stimuli responsiveness. While increasing their hydrophobicity is connected to phase inversion from oil-in-water (O/W) to water-in-oil (W/O) emulsions, a predictive model to relate this phase inversion to the molecular structure of the nano/microgel network remains missing. Addressing this challenge, we developed a library of amphiphilic nanogels (ANGs) that enable adjusting their hydrophobicity while maintaining similar colloidal structures. This enabled us to systematically investigate the influence of network hydrophobicity on emulsion stabilization. We found that W/O emulsions are preferred with increasing ANG hydrophobicity, oil polarity, and oil/water ratio. For nonpolar oils, increasing emulsification temperature enabled the formation of W/O PEs that are metastable at room temperature. We connected this behavior to interfacial ANG adsorption kinetics and quantified ANG deformation and swelling in both phases via atomic force microscopy. Importantly, we developed a quantitative method to predict phase inversion by the difference in Flory–Huggins parameters between ANGs with water and oil (χwater – χoil). Overall, this study provides crucial structure–property relations to assist the design of nano/microgels for advanced PEs.