The application of a multisensor system to groundwater monitoring is investigated. The sensor system is based on an array of non-specific potentiometric chemical sensors with data processing by artificial neural networks and includes 13 sensors with PVC membranes and 12 solid-state ones. Results of measurements in model solutions containing heavy metals, alkali- and alkali-earth cations and inorganic anions at concentrations typical for groundwater near the city of Braunschweig, Germany, are presented. Both the response of the whole sensor array and the responses of subsystems consisting only of PVC and only of solid-state sensors, respectively, are investigated. It is shown that both subsystems can be used for determination of described ions and that the best results are obtained if the whole array of sensors is used.