To develop biodegradable composite films with fresh-keeping effects, caffeic acid (CA) was covalently grafted with amino-mesoporous silica nanoparticles (NH₂-MSN) via a carbodiimide mediated coupling reaction and loaded with eugenol (EG) to obtain eugenol/caffeic acid-mesoporous silica nanoparticles (EG/CA-MSN). Zein was used as film-forming matrix and EG/CA-MSN used as functional filler. Eugenol/caffeic acid-mesoporous silica nanoparticles/Zein (EG/CA-MSN/Zein) composite films were further obtained by flow casting method. The effects of the added amount of EG/CA-MSN on the physicochemical and functional properties of the composite films were investigated. SEM and FTIR results showed that EG/CA-MSN demonstrated good biocompatibility and intermolecular interactions with zein film matrix. The addition of EG/CA-MSN could improve the barrier properties and mechanical properties of the composite films. When the mass fraction of EG/CA-MSN was 9%, and the water vapor transmission rate of composite films was the lowest [3.11×10-9g· mm/(m²·s·Pa)],the tensile strength could reach 18.86MPa,which was significantly better than the single zein film. When the mass fraction of EG/CA-MSN was 12%,the composite films demonstrated decent antioxidant and bacteriostatic properties. The free radical scavenging rate of DPPH and ABTS⁺ increased to 78.28% and 85.49%,respectively. The diameter of inhibition zone against Escherichia coli and Staphyloccus aureus reached 13.57mm and 12.38mm,respectively. The application of the composite films in the preservation of frozen fillets could effectively delay the total volatile basic nitrogen and fat oxidation during storage. The developed EG/CA-MSN/Zein composite film had potential applications value in the preservation of aquatic products.