Interfacial self-assembly has become a powerful force for regulating the amphipathy of Pickering emulsions on the oil/water interface. Herein, metal–phenolic supramolecular coatings, acting as a regulator on the oil/water interface, were fabricated on the surface of zein nanoparticles (NPs), as a consequence of which the prepared Pickering emulsions stabilized by the decorated zein NPs exhibited diverse properties, decided by different concentrations of zein, tannic acid (TA), and metal ions (Fe3+). Metal–phenolic network-decorated zein NPs named ZTFex NPs (ZTFe NPs represented zein/TA/Fe3+ NPs, and x represented different concentrations of compounds) exhibited increasing diameters of 100–110 nm. Three-phase contact angles also showed that the strong hydrophobicity of zein NPs could be decreased as a result of the formation of metal–phenolic networks. As for corresponding Pickering emulsions, the covering of TA–Fe3+ networks on zein NPs could enhance the stability of zein NP-based emulsion obviously, which might be due to the fact that ZTFex NPs revealed the ability to form strong films on the oil/water interfaces. ZTFe4 was selected as an optimal concentration because of its minimum size and excellent storage stability. Besides, it was also found that the diameter of ZTFe4-based emulsion enhanced with the increase in the oil phase. The rheological measurement results showed that both G′ and G″ increased with the increase of x and the oil phase. In general, our paper not only highlighted a straightforward method for the interfacial nanofabrication of solid particles but also provided a novel and potential strategy in Pickering emulsion applications.