AbstractPolyolefins functionalized with diethylmaleate were mixed with poly(vinylchloride) (PVC) in different compositions. Intermolecular interactions involving the carbonyl groups of the side chains of the functionalized polyolefins and methine hydrogens of PVC were investigated by means of infrared spectroscopy. The major flexibility of the ester groups attached to the backbone chains, with respect to polyesters, seems to increase the capability of such groups to interact with groups of more polar polymers, thus allowing prediction of easier miscibility, which however also depends on the starting polyolefin structure and function‐alization degre