Bacterial infections have consistently posed a significant danger to public health. It is crucial to develop effective antibacterial agents from natural polymers. In this study, we propose a novel approach by combining dextrin and polyvinyl alcohol (PVA) to create an effective iodine delivery system with enhanced antimicrobial properties and biocompatibility, showing strong potential for wound management applications. Dextrin/PVA/iodine complexes were prepared by dissolving dextrin and PVA in water, followed by the addition of an iodine solution. The samples were characterized using ultraviolet-visible spectroscopy, Fourier transform infrared spectroscopy, proton nuclear magnetic resonance spectroscopy, and X-ray diffraction methods, confirming that the dextrin/PVA/iodine complexes were successfully prepared. Thermogravimetric (TG) analysis indicated that the chemical modification of dextrin and iodine complexation reduced the thermal stability; titration analysis revealed that 95% of the iodine in the dextrin/PVA/iodine complex was in the form of triiodide ions. The iodine contents of the three dextrin/PVA/iodine complexes (D/PVA/I-1, D/PVA/I-2 and D/PVA/I-3) were 4.27 ± 0.15%, 2.49 ± 0.18%, and 0.79 ± 0.21%, respectively. The antibacterial effects were evaluated in vitro against reference strains Staphylococcus aureus ATCC BAA-39, Staphylococcus aureus ATCC BAA-33591, Streptococcus pneumoniae ATCC BAA-660, Esсherichia coli ATCC BAA-196, Esсherichia coli ATCC BAA-2524, Acinetobacter baumannii ATCC BAA-1790, Klebsiella pneumoniae ATCC 700603, Klebsiella pneumoniae ATCC 2524 and clinical isolates Streptococcus pneumoniae SCAID PHRX1-2018, Esсherichia coli SCAID WND1-2021, Pseudomonas aeruginosa SCAID PHRX1-2019 and Pseudomonas aeruginosa TA2. The results demonstrated that the dextrin/PVA/iodine complexes exhibited strong antibacterial activity against both reference and clinical strains, effectively inhibiting their growth. In particular, D/PVA/I-1 exhibited the best antibacterial effect. In a comparative analysis of the CTC50 of substances D/PVA/I-1, D/PVA/I-2 and D/PVA/I-3 using Tukey's multiple comparison test, no statistically significant differences were found among the groups. Therefore, CSAN-I complexes can be considered as promising candidates for wound management in clinical applications.