Ionically self-assembled monolayer (ISAM) films are a recently developed class of materials that allows detailed structural and thickness control at the sub-nanometer level combined with ease of manufacturing and low cost. The ISAM fabrication method simply involves the dipping of a charged substrate alternately into polycationic and polyanionic aqueous solutions at room temperatures. Importantly, the ISAM technique yields exceptionally homogeneous, large area films with excellent control of total film thickness. We describe detailed studies of ISAM light emitting diodes incorporating poly(para-phenylene vinylene) (PPV) as the light emitting polymer. The individual thickness of each monolayer and the interpenetration of adjacent layers can be precisely controlled 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. The ISAM process also allows the advantage of depositing well-defined thicknesses of separate polymers at the indium tin oxide and the aluminum electrode interfaces.