High internal phase Pickering emulsions (HIPPEs) have taken a center stage in the arena of delivery systems in the food industry because of their high loading capacity and stability. In addition, metal-organic frameworks (MOFs), a type of cutting-edge designable porous scaffolding material, have attracted attention in reticular chemistry, which satisfies fundamental demands for delivery research in the past years. Here, we demonstrate a novel metal-organic framework (MOF)-stabilized HIPPE delivery system for hydrophobic phytochemicals. First, a novel high-biocompatibility and stable MOF particle, UiO-66-NH2, was selected from atomic simulation screening, which showed proper electronegativity and amphiphilic properties to develop the HIPPE system. Monodispersed UiO-66-NH2 nanoparticles with the particle size of 161.36 nm were then prepared via solvothermal synthesization. Pickering emulsions with inner phase ratios from 50 to 80% with varied contents of polyethylene glycol (PEG) were prepared by in situ high-pressure homogenization, and their physicochemical properties including crystallography, morphology, and rheology were systematically characterized. Subsequently, curcumin, a model antioxidant, was loaded in the HIPPE system and named cur@UiO-66-NH2/HIPPE. It exhibited high loading capacity, up to 6.93 ± 0.41%, and encapsulation efficiency (19.76 ± 3.84%). This novel MOF nanoparticle-stabilized HIPPE delivery system could be practically utilized for other bioactive components and antimicrobial agents, which would find applications in food safety and biomedical areas in the future.