We present detailed studies of polymer light emitting diodes fabricated from ionically self-assembled monolayer thin films. The ionically self-assembled monolayer (ISAM) films are created with a new thin film fabrication technique that allows detailed structural and thickness control at the molecular level. The ISAM fabrication method simply involves the dipping of a charged substrate alternately into polycationic and polyanionic aqueous solutions at room temperature. Importantly, the ISAM technique yields exceptionally homogeneous, large area films with excellent control of total film thickness. Our studies concentrate on improving the performance of ISAM light emitting diodes that include poly(para-phenylene vinylene) (PPV). The individual thickness of each monolayer and the interpenetration of adjacent layers can be precisely manipulated through the parameters of the electrolyte solutions. The effects of the pH and ionic strength of the immersion solutions, the total film thickness, and the PPV thermal conversion parameters on the photoluminescence and electroluminescence yields have been systematically studied. Through the ISAM process we can also deposit well-defined thicknesses of different polymers at the indium tin oxide and aluminum electrode interfaces. The interface layers are found to affect the electroluminescence efficiency.