All-solid-state copper, cadmium and thallium sensors based on chalcogenide thin film layers prepared by means of the pulsed laser deposition (PLD) technique have been developed. The sensitive layers have been investigated using Rutherford backscattering spectrometry (RBS) and transmission electron microscopy (TEM). The electrochemical behaviour of the sensors in terms of ionic sensitivity, limit of detection, Nernstian response interval, the effect of the pH, selectivity coefficients, dynamic response time and drift has been evaluated. The results of copper, cadmium and nickel analysis in industrial solutions using the developed sensors are presented.