Basic characteristics of on-line extractive fermentation of organic acids were examined using a general model for the integrated process in order to illustrate the effects of various process parameters and operational modes on system performance. The strong pH dependence of both the fermentation kinetics and the extraction efficiency has been outlined and taken into account by inclusion of a model equation which predicts the pH profile. Simulation results using data from butyric acid fermentations show that our complete model system is adequate to evaluate different operational modes of the process, including simple batch fermentation, batch or fed-batch fermentation with extractive recycle, and continuous fermentation with extractive recycle. In the case where a second undesired acidic byproduct is also produced, our model predictions suggest that on-line extractive fermentation using a suitable solvent results in an effective gross separation of the two acids.