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Surface hydrophobicity and grease resistance of paper may be achieved by the application of coatings usually derived from fossil-oil resources. However, poor recyclability and environmental concerns on generated waste has increased interest in the study of alternative paper coatings. This work focuses on the study of the performances offered by two different biopolymers, poly(3-hydroxybutyrate-co-3hydroxyvalerate) (PHBV) and polycaprolactone (PCL), also assessing the effect of a plasticizer (PEG) when used as paper coatings. The coated samples were characterized for the structural (by scanning electron microscopy, SEM), diffusive (water vapor and grease barrier properties), and surface properties (affinity for water and oil, by contact angle measurements). Samples of polyethylene-coated and fluorinated paper were used as commercial reference. WVTR of coated samples generally decreased and PHBV and PCL coatings with PEG at 20% showed interesting low wettability, as inferred from the water contact angles. Samples coated with PCL also showed increased grease resistance in comparison with plain paper. This work, within the limits of its lab-scale, offers interesting insights for future research lines toward the development of cellulose-based food contact materials that are fully recyclable and compostable.