The demand for online monitoring and control of biogas process is increasing, since better monitoring and control system can improve process plants stability and economy. A number of parameters in both the liquid and the gas phase have been suggested as process indicators (pH, alkalinity, VFA and H-2, redox potential, biogas production rate, biogas composition, FOS/TAC ratio, COD and/or VS reduction). The present study proposes the use of complex sensors as a possible solution to engineer a consistent control system. Tests were performed to analyze the biogas coming from a biogas plant in which conditions of pre-overloading and overloading were artificially inducted. The different inducted functioning conditions were recognised using a FOS/TAC tester, or the ratio volatile organic acids/alkaline buffer capacity. The FOS/TAC ratio has long been recognized extending as far as the imminent inversion of the digester biology to be detected at an early stage. Data coming from the e-nose were sorted and classified according to FOS/TAC ratio as a reference method. Not all the sensors of the e-nose were reactive to manure digestates, but four of them, sensitive to aromatic compounds, ammonia alkanes and methane, resulted crucial in the samples identification. Results confirmed that the e-nose can discriminate different digestion conditions, demonstrating the possibility to reduce the number of sensors in this innovative tool for biogas control systems. However, this instrument cannot be considered a complete alternative to traditional analysis systems, as, for example, the FOS/TAC titration, but a supporting tool for a quick analysis of the system.