Blended films were obtained from polyvinyl alcohol‐co‐ethylene (EVOH) with 52 kDa weight average molecular weight (Mw) and three water soluble biopolymers isolated from exhausted tomato plants hydrolysates. Two biopolymers contained mainly polysaccharides and had 27 and 79 kDa Mw, respectively. The third contained mainly lignin‐like C moieties and had 392 kDa MW. The films were fabricated with a biopolymer/EVOH w/w ratio ranging from 0.1 to 0.9. All blends had molecular weight and solubility which were substantially different from the starting materials. They were characterized for the chemical nature, and the thermal, rheological, and mechanical properties. Evidence of a chemical reaction between the biopolymers and EVOH was found. Generally, the films exhibited higher mechanical strength but lower strain at break then the neat EVOH. The best performing blended film was fabricated from the 27 kDa Mw polysaccharide. This contained less than 10% biopolymer. It exhibited 1043 MPa Young's modulus and 70% strain at break against 351 MPa modulus and 86% strain for neat EVOH. The results offer scope for investigating biopolymers sourced from other biowastes to understand more the reasons of the observed effects and exploit their full potential to modify or to replace synthetic polymers.