In this study, for the first time, Epilobium parviflorum Schreb. (E, hoary willowherb) aqueous extract was introduced into edible biopolymer films and its influence on physicochemical properties of the final products were investigated. Potato starch was gelatinized in the herbal tea to obtain thermoplastic starch (TPS) films via the casting method. The characterization of the films included mechanical, antioxidative, water (WVTR, contact angle, swelling degree) and UV radiation barrier properties as well as microstructure analysis (SEM). Obtained results indicated that the presence of the extract (rich in phenolic compounds) in the films acted as a co-plasticizer for starch and led to a higher elongation at break, up to 70%, with a parallel increase in tensile strength up to ca. 9 MPa. Moreover, TPS films with E exhibited lower WVTR values and absorption of UV light in comparison with the control TPS film. DPPH scavenging activity of TPS E films immersed in methanol was ca. 92%, and it was related to the release of the extract into liquid media. Novel TPS E films are characterized by multifunctional properties that can be used, e.g., in the active packaging sector.