Effects of ion concentration and active layer thickness play a critical role on the performance of light-emitting electrochemical cells. Expanding on a pioneering materials system comprising the super yellow (SY) polymer and the electrolyte trimethylolpropane ethoxylate (TMPE)/Li⁺CF₃SO₃⁻, it is reported that a slightly lowered salt concentration and layer thickness result in a substantial efficiency increase, and that this increase is confined to a narrow concentration and thickness range. For a film thickness of 70 nm, a blend ratio SY:TMPE:Li⁺CF₃SO₃⁻ = 1:0.075:0.0225, and a current of 7.7 mA cm⁻² the current efficacy is 11.6 cd A⁻¹, on a par with SY light-emitting diodes. The optimized salt content can be explained by increased exciton quenching at higher concentrations and hindered carrier injection and conduction at lower concentrations, while the optical dependence on the layer thickness is due to weak microcavity effects. A comprehensive optical modeling study is presented, which includes the doping-induced changes of the refractive indices and self-absorption losses due the emission–absorption overlap of intrinsic and doped SY. The analysis indicates either a thickness-independent emitter position (EP) close to the anode or a thickness-dependent EP, shifted to the cathode for increased thicknesses.