Abstract Manufacturing of glass/ITO/PEDOT:PSS/MEH-PPV/PEDOT:PSS/Al organic light emitting diode (OLED) by depositing PEDOT:PSS/MEH-PPV/PEDOT:PSS using spin coating has been reported. The roles of PEDOT:PSS in the structure have been reported. It allows transportation of holes from ITO to the highest occupied molecular orbit (HOMO) of MEH-PPV. In additions, it allows transportation of electrons from Al to lowest unoccupied molecular orbit (LUMO) of MEH:PPV. Further, it confines electrons in the LUMO of MEH:PPV due to the higher barrier of PEDOT:PSS of LUMO. The effect of thermal annealing on the current-voltage curve as well as on the electroluminescence intensity has been reported. The results show that the current increased from 25 mA to 52 mA at 7 V, when the sample was thermally annealed at 150 °C. Such enhancement in electrical injection leads to enhancement of the electroluminescence to a factor of 4.7 at the peak luminescence wavelength (∼592 nm). Reasons for electroluminescence improvement caused by thermal annealing have been proposed.