This work attempted to engineer emulsions’ interface using the special affinity between proline-rich gliadin and proanthocyanidins (PA), to develop surfactant-free antioxidant Pickering emulsions with digestive-resistant properties. This binding interaction between gliadin and PA benefited the interfacial adsorption of the particles to corn oil droplets. Pickering droplets as building units assembled into an interconnected three-dimensional network structure, giving the emulsions viscoelasticity and ultrastability. Oxidative markers in Pickering emulsions were periodically monitored under thermally accelerated storage. Lipid digestion and oxidation fates were characterized using in vitro gastrointestinal (GI) models. The interfacial membrane constructed by antioxidant particles served as a valid barrier against lipid oxidation and digestion, in a PA dose-dependent manner. Briefly, lipid oxidation under storage and simulated GI tract was retarded. Free fatty acid (FFA) fraction released decreased by 55% from 87.9% (bulk oil) to 39.5% (Pickering emulsion), implying engineering interfacial architecture potentially benefited to fight obesity. This study opens a facile strategy to tune lipid oxidation and digestion profiles through the cooperation of the Pickering principle and the interfacial delivery of antioxidants.