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Saltwater Intrusion (SWI) is threatening coastal archaeological sites, particularly in Crotone, southern Italy. The study area has been experiencing notable SWI due to over-pumping of groundwater, rising land subsidence, and climate change. Consequently, this study examines the applicability of polycaprolactone (PCL), commonly a biodegradable polymer, as a protective barrier for archaeological conservation. PCL films were synthesized via solvent casting and dried under controlled conditions. Physicochemical properties of the films were evaluated using six analytical techniques: (1) contact angle measurements for surface hydrophobicity, (2) Fourier-Transform Infrared Spectroscopy (FTIR) for chemical stability, (3) Scanning Electron Microscopy (SEM) for morphological characterization, (4) permeability testing for evaluating saltwater diffusion, (5) mechanical testing for tensile properties, and (6) biodegradability assays for degradation rates. All samples were evaluated at 0, 30, 60, and 90 days in natural seawater. Results from these tests indicate that unmodified PCL films exhibit moderate hydrophobicity, low chemical stability, moderate permeability, declining mechanical strength, and limited biodegradability over the testing period. Therefore, their suitability as long-term protective barriers requires further optimization. Nevertheless, material enhancement using nanoparticles or surface functionalization is highly recommended to improve hydrophobicity, enhance surface stability, reduce permeability, decrease biodegradability, and increase durability in saline environments.