Pectin and ε-polylysine (ε-PL) nanoparticles loaded with Litsea cubeba essential oil (LEO) (PP-LNPs) were prepared through the electrostatic interaction. Metal phenol network (MPN) coatings, designated as MPN@PP-LNPs, were fabricated on the surface of the nanoparticles via self-assembly process of tannic acid (TA) and FeIII to develop food preservative materials with pH-responsive controlled release. The morphology, encapsulation efficiency, and pH-responsive release characteristics of MPN@PP-LNPs were investigated. The results showed that the particle size of MPN@PP-LNPs was 432.5 ± 58.6 nm. Furthermore, the encapsulation efficiencies of ε-PL and LEO were 83.26 ± 2.21% and 30.78 ± 3.92%, respectively. TA was rapidly released at low pH, while LEO exhibited controlled release over a wide pH range (pH 1.2–9.0). In addition, the MPN coating has been demonstrated to enhance antioxidant activity and inhibit the growth of E. coli and S. aureus under acidic conditions. Furthermore, preliminary evidence suggests that MPN@PP-LNPs are not cytotoxic. In conclusion, MPN@PP-LNPs, prepared through the self-assembled surface modification of TA and FeIII, was an effective material for food preservation.