There are presented results of investigation of electrostatic separation of binary mixtures containing a biodegradable polymer {polylactide (PLA), polycaprolactone (PCL), or poly(3-hydroxybutyrate-co-4-hydroxybutyrate) [P(3,4HB)]} and a commonly used polymer [poly(vinyl chloride) (PVC) or poly(ethylene terephthalate) (PET)]. It was found that the binary mixtures of these polymers could be efficiently separated. The electrostatic separation process of the P(3,4HB)/PET mixture appeared to be most successful. It is indicated that the share of a biodegradable component in the mixture essentially influences the separation effects. Therefore, suitable choice of necessary conditions is needed to perform the separation process, which includes appropriate separator settings, depending on fractions of individual components in the mixture being separated.