This research investigated the use of an innovative polytetrafluoroethylene (PTFE) membrane configuration coupled to electrodialysis for the in-situ removal of Volatile Fatty Acids (VFAs) from a mixed culture bioreactor. It was shown that by stacking the PTFE membranes to increase the active membrane surface area, shortened VFA recovery times was seen. The addition of electrodialysis to the PTFE membrane stack enabled the continuous extraction of VFAs from fermentation media whilst retaining essential nutrients and organic compounds in the diluate stream. Ammonium, phosphate and nitrate remained in the diluate chamber and did not cross the PTFE membrane stack. Up to 98% of total VFA recovery was achieved with the PTFE and electrodialysis system. The process was shown to extract from a reservoir of low VFA concentration to a reservoir with a VFA concentration 10 times higher. These results show that the addition of electrodialysis to PTFE provides a robust solution for the in-situ extraction of VFAs from fermentation media within bioreactors to support the demand for sustainable fuels and green chemical feedstocks.