Nowadays, the merging of membrane and fermentation technologies is receiving significant attention such as in the case of itaconic acid (IA) production, which is considered as a value-added chemical. Its biotechnological production is already industrially established; however, the improvements of its fermentative and recovery steps remain topics of significant interest due to sustainable development trends. With an adequate downstream process, the total price of IA production can be reduced. For the task of IA recovery, a contemporary electro-membrane separation processes, electrodialysis with bipolar membranes (EDBM), was proposed and employed in this work. In the experiments, the laboratory-scale, commercialized EDBM unit (P EDR-Z/4x) was operated to separate IA from various model solutions compromised of IA (5−33 g/L), glucose (varied in 15−33 g/L as a residual substrate during IA fermentation) and malic acid (varied in 0−1 g/L as a realistic by-product of IA fermentation) under different initial pH (2−5) and applied potential conditions (10−30 V). Unambiguously negative effects related to the glucose and malic acid as impurities were found neither on the IA recovery ratio nor on the current efficiency, falling into the ranges of 90−97% and 74.3−98.5%, respectively. The highest IA recovery ratios of 97% and 98.5% of current efficiency were obtained with the model fermentation solution containing 33 g/L IA, 33 g/L glucose at 20 V and an initial pH of 5. However, the selective separation of IA needs further investigations with a real fermentation broth, and the findings of this research may contribute to further studies in this field.