Nowadays, the shelf-life extension of foods is a topic of major interest because of its environmental and economic benefits. For this purpose, various methods like deep-freezing, ultra-high-temperature pasteurization, drying methods, use of chemicals, controlled-atmosphere preservation, ionizing irradiation, and were investigated. During the last years, the smart packaging for foods using natural biodegradable components is of great interest because it provides positive environmental fingerprint and high shelf-life extension. In the present work, a new nanostructured composite material, the ZnO/Na-Montmorillonite hybrid, was developed. The high antimicrobial properties of the 3-D ZnO material in combination with the high barrier and strength properties of the 2-D Na-Montmorillonite material provided a high promising component for food smart packaging applications. As an extra innovation of this process, the ZnO nanorods coated the external surface of the Na-Montmorillonite and it was not intercalated into the clay as a pillaring material. This new material was incorporated with a 3% w/w composition with a biodegradable poly(vinyl)alcohol (PVOH) polymeric matrix which also exhibits antimicrobial activity. The final product was tested via XRD, FTIR, SEM, tensile test, water sorption, water vapor permeability, oxygen permeability UV–vis, and anti-microbial activity tests and it exhibited advanced mechanical and antimicrobial properties, especially for a ZnO/Na-Montmorillonite fraction of 4:1.