Poly(vinyl alcohol) (PVA)/chitosan (CS)/montmorillonite (C30B) materials for food packaging applications were prepared by using a noninvasive and low-cost freeze/thawing method. Cloisite 30B nanoclay content in PVA/CS gels was varied in order to establish optimum amount to obtain improved properties. The structural, morphological, rheological aspects, thermal stability, and antimicrobial activity were investigated using various techniques as Fourier transform infrared, scanning electron microscopy, rheology, thermogravimetric analysis, differential scanning calorimetry, dynamic mechanical thermal analysis, and antibacterial tests. It was noticed that the obtained materials show an intercalated structure with specific interactions between components and nanoclay incorporation led to an increased thermal stability, mechanical properties, and excellent antimicrobial activity against Escherichia coli, Listeria monocytogenes, and Salmonella typhimurium due to synergistic action of CS and nanoclay.