Toxic metal elements in waters and wastewaters contaminate the environment and greatly threaten the health of human beings, therefore developing a rapid monitor for metal residues in aqueous solutions is urgently required．In the present work, a new homemade apparatus of electrolyte cathode atmospheric glow discharge emission spectroscopy was developed and described. It can detect and discriminate many kinds of trace mental elements by atomic emission spectrum from atmospheric pressure liquid cathode glow discharge. In order to estimate the analytical performance of the present atmospheric pressure electrolyte cathode glow discharge emission spectroscopy system, the detection limit values for Na, Li, Cu, Pb and Mn were obtained based on 3σ of the background signal, and the current limits of detection were 0.008, 0.005, 1.1, 2.06 and 1.95 mg·L-1, respectively. It demonstrates that the atmospheric pressure electrolyte cathode glow discharge emission spectroscopy has a promising application in real time measurements of metal residues in aqueous solutions.