Given recent worldwide environmental concerns, biodegradability, antibacterial activity, and healing properties around the wound area are vital features that should be taken into consideration while preparing biomedical materials such as wound dressings. Some of the available wound dressings present some major disadvantages. For example, low water vapor transmission rate (WVTR), inadequate exudates absorption, and the complex and high environmental cost of the disposal/recycling processes represent such drawbacks. In this paper, starch/polyvinyl alcohol (PVA) material with inserted nano-sized zinc-oxide particles (nZnO) (average size ≤ 100 nm) was made and altered using citric acid (CA). Both ensure an efficient antibacterial environment for wound-dressing materials. The film properties were assessed by UV–Vis spectrometry and were validated against the UV light transmission percentage of the starch/ polyvinyl alcohol (PVA)/ zinc-oxide nanoparticles (nZnO) composites. Analyses were conducted using X-ray Spectroscopy (EDX) and scanning electron microscopy (SEM) to investigate the structure and surface morphology of the materials. Moreover, to validate an ideal moisture content around the wound area, which is necessary for an optimum wound-healing process, the water vapor transmission rate of the film was measured. The new starch-based materials exhibited suitable physical and chemical properties, including solubility, gel fraction, fluid absorption, biodegradability, surface morphology (scanning electron microscopy imaging), and mechanical properties. Additionally, the pH level of the starch-based/nZnO film was measured to study the prospect of bacterial growth on this wound-dressing material. Furthermore, the in vitro antibacterial activity demonstrated that the dressings material effectively inhibited the growth and penetration of bacteria (Escherichia coli, Staphylococcus aureus).