The valorization of potato peel side streams for food packaging applications, especially for the substitution of current petrochemical-based oxygen barrier solutions such as EVOH, is becoming increasingly important. Therefore, potato peel-based films and coatings (on PLA) were developed containing 10–50% (w/w potato peel) citric acid (CA). To determine the impact of CA concentration on the structure and physicochemical properties of cast films and coatings, ATR-FTIR spectroscopy, moisture adsorption isotherms, tensile properties, light transmittance, oxygen permeability, carbon dioxide transmission rate, and water vapor transmission rate measurements were performed. The results indicate that an increase in CA concentration from 10% to 30% increased esterification/cross-linking and resulted in minimal values for the oxygen permeability (0.08 cm3 m−2 d−1 bar−1) at 50% RH and water vapor transmission rate (1.6 g m−2 d−1) at 50% → 0% RH, whereas an increase from 30% to 50% increased free CA concentration and resulted in increased flexibility, indicating that CA functioned as a plasticizer within the film/coating at higher concentrations. Overall, potato peel-based coatings containing CA showed comparable barrier properties to EVOH. We assume that an extensive industrial purification or fractionation of potato peel, which was not carried out in this study, could lead to even lower transmission rates.