Biomedical industries are attempting to utilize natural materials, as they are bio-compatible, non-toxic, and show bioactive properties, like antimicrobial activity. In this study, natural polyelectrolyte complexed chitosan/alginate films (PECs) were prepared via a casting/solvent evaporation technique, and their characteristics and drug release properties were investigated. PEC films made with two different overall polymer contents, 0.4 and 1 w/v%, were loaded with thyme oil nanoemulsion as drug carrier. The structure of the films was studied by FTIR and optical and scanning electron microscopy. Prepared PEC films had good mechanical and water vapor permeability properties. Release of the thyme oil from the pH-sensitive PEC films (TM-PEC) was detected and followed by UV spectroscopy. The results indicated that the drug release rate of TM-PEC films was the fastest when the chitosan content was 1 %w/v, and various mathematical models were analyzed for investigating the drug release mechanism. Antibacterial tests were performed by counting the number of surviving gram-negative and gram-positive bacteria. The in vitro test indicated the limitation Escherichia coli (E. coli) and Staphylococcus aureus (S.aureus) growth in the presence of TM-PEC films. The MTT test showed more cell viability of the TM-PEC film in comparison with that of the PEC film without TM. Based on the measured physical and antibacterial properties, the chitosan–alginate PEC films loaded with antibacterial essential oils can be considered for biomedical applications, such as wound dressings or controlled release systems.