Wound infection exacerbated by multidrug-resistant (MDR) bacteria has necessitated the need for wound dressing materials with embedded antimicrobial property to prevent the development of chronic wounds. Iodine (I₂), typically as a poly(vinyl pyrrolidone)-I₂ (PVP–I) complex, is a widely used antiseptic agent in wound care owing to its efficacy, safety, and low probability to cause further resistance. Despite extensive research on PVP–I formulations, there is potentially a large selection of poly(vinyl amide)s that have remained largely unexplored as iodophoric materials, particularly as coatings for wound dressings and medical devices. Therefore, in this study we prepared a series of stable, cross-linked poly(vinyl amide) coatings via plasma polymerization and studied their structure–property relationships for the complexation and release of I₂. Plasma polymerized poly(N-vinyl-2-pyrrolidone) (pPVP), poly(N-methyl-N-vinylacetamide) (pPMVA) and poly(N-vinylcaprolactam) (pPVCl) nanoscale coatings were prepared with uniform thicknesses of 330–340 nm and low surface roughness. Complexation of I₂ as polyiodides resulted in a significant increase in the pPVCl coating thickness in phosphate buffered saline (PBS), consistent with the Hofmeister effect. Raman spectroscopy confirmed that the I₂ was complexed exclusively as the triiodide ion (I₃^-) in all coatings, which was confirmed by synchrotron X-ray photoelectron spectroscopy (XPS) experiments. Nuclear magnetic resonance (NMR) spectroscopy of poly(vinyl amides) was employed to further prove that the complexing species was hydrogen triiodide (HI₃). The loading of I₂ species increased from pPVP < pPMVA < pPVCl, with percentage elemental compositions of 1.3, 1.8, and 2.9%, respectively, which correlated with the extent of nitrogen loss during polymerization and oxidation, and was also in agreement with determined negative zeta potential values. However, quantification of the released I₂ species over 5 h showed that the greatest release was observed from pPMVA (121.3 µg.cm⁻²), with pPVP (77.4 µg.cm⁻²) and pPVCl (74.6 µg.cm⁻²) releasing a similar amount, highlighting that I₂ release from poly(vinyl amide) coatings is a function of the loading and composition of the polymer, not just the I₂ complexing amide motif. The I₂ complexed pPMVA coated wound dressings were highly effective against Gram-negative Pseudomonas aeruginosa and Gram-positive Staphylococcus aureus, the two major strains associated with wound infection, reducing bacterial viability by up to 4 and 7 (log₁₀ reduction) orders of magnitude. Overall, the poly(vinyl amide) coatings are promising iodophors for the prevention and treatment of wound infections.