A cathode system comprising an ultra thin sodium chlorate (NaCl) layer and an overlaid calcium (Ca) metal in polymer light-emitting diodes (PLEDs) based on poly[2-methoxy,5-(2-ethylhexoxy)-1,4-phenylene vinylene] is presented. It is demonstrated that introducing a thin NaCl layer further improves the brightness and electroluminescent efficiency of PLEDs. The maximum brightness and efficiency, respectively, reached 22 000 cd/m(2) and 3.5 lm/W for PLEDs with a 1 nm NaCl layer, which are much higher than 18 500 cd/m(2) and 2.0 lm/W for PLEDs with Ca cathode. The investigation of the electron injection in electron-only devices with and without a NaCl layer indicates that the introduction of the NaCl layer substantially enhances the electron injection current, which in case of PLEDs leads to the improvement of the brightness and efficiency. (c) 2005 Elsevier B.V. All rights reserved.