A new method of continuous process analysis in fermentation using a mass spectrometer (MS) membrane probe is described. A number of samples from industrial fermentations were analyzed for the occurrence of volatiles detectable with a silicone membrane probe connected to a quadrupole MS. In all fermentations, characteristic spectra were observed which were found to change systematically during the batch process. Factor analysis was used to treat the data. The factor scores were compared with the actual product concentrations (antibiotics, toxins, etc.), which were measured using other analytical methods and were found to correlate with them. On-line analysis was also carried out on a fermentation with an MS and an Apple II microcomputer. Direct monitoring of products, which are not directly measurable with the membrane MS probe requires a new calibration each time conditions such as medium composition are changed.