The work presented here describes the first results of an effective method of assessing the quality of electrostatic separation of mixtures of polymer materials. The motivation for the research was to find an effective method of mechanical separation of plastic materials and a quick assessment of the effectiveness of the method itself. The proposed method is based on the application of a dedicated vision system developed for needs of research on electrostatic separation. The effectiveness of the elaborated system has been demonstrated by evaluating the quality of the separation of mixtures of poly (methyl methacrylate) (PMMA) and polystyrene (PS). The obtained results show that the developed vision system can be successfully employed in the research on plastic separation, providing a fast and accurate method of assessing the purity and effectiveness of the separation process.