Understanding “efficiency roll‐off” (i.e., the drop in emission efficiency with increasing current) is critical if efficient and bright emissive technologies are to be rationally designed. Emerging thin‐film light‐emitting electrochemical cells (LECs) can be cost‐ and energy‐efficiently fabricated by ambient‐air printing by the virtue of the in‐situ formation of a p‐n junction doping structure. However, this in‐situ doping transformation renders a meaningful efficiency analysis challenging. Herein, a method for separation and quantification of major LEC loss factors, notably the outcoupling efficiency and exciton quenching, is presented. Specifically, the position of the emissive p‐n junction in common singlet‐exciton emitting LECs is measured to shift markedly with increasing current, and the influence of this shift on the outcoupling efficiency quantified. It is further verified that the LEC‐characteristic high electrochemical‐doping concentration renders singlet‐polaron quenching (SPQ) significant already at low drive current density, but also that SPQ increases super‐linearly with increasing current, because of increasing polaron density in the p‐n junction region. This results in that SPQ dominates singlet‐singlet quenching for relevant current densities, and significantly contributes to the efficiency roll‐off. This method for deciphering the LEC efficiency roll‐off can contribute to a rational realization of all‐printed LEC devices that are efficient at bright luminance.This article is protected by copyright. All rights reserved