With the aim of enhancing electron injection in organic electronic devices, a self- assembled monolayer (SAM) that reacts with both cathode and polymer insulating nanolayers was used. The turn-on voltage of the device decreased from 16 to 7 V by inserting a methoxy-terminated SAM between the cathode and polymer insulating nanolayer. Synchrotron radiation photoelectron spectroscopy results showed that inserting the SAM and polymer insulating nanolayer caused the work function to decrease by about 0.8 eV. This reduction lowers the electron injection barrier, and produces a decrease in turn- on voltage of the device. (c) 2006 The Electrochemical Society.