Electrochemical parameters of sensor response of various chalcogenide glass sensor materials have been studied in solutions of heavy metal cations. The principle attention have been paid to non-specific sensor response characteristics including cross-sensitivity. The dependence between the cation sensitivity and selectivity of the sensor material and the nature of glass-former, especially chalcogen, sulphur or selenium, has been observed. The solid-state chalcogenide glass sensors were included, together with some conventional crystalline sensors into an array (a multisensor system). The array was trained in complex composition solutions, containing Cu2+, Pb2+, Cd2+, Zn2+, Cl−1, F− and SO42− in concentration typical for industrial waste. It was found that such an approach allows all the species in the mixed solutions to be to determined in spite of insufficient selectivity of some sensors. Also, it appeared possible to determine zinc and sulphate for which no selective sensors were present in the array.