In light-emitting electrochemical cells (LECs), the position of the emission zone (EZ) is not predefined via a multilayer architecture design, but governed by a complex motion of electrical and ionic charges. As a result of the evolution of doped charge transport layers that enclose a dynamic intrinsic region until steady state is reached, the EZ is often dynamic during turn-on. For thick sandwich polymer LECs, a continuous change of the emission color provides a direct visual indication of a moving EZ. Results from an optical and electrical analysis indicate that the intrinsic zone is narrow at early times, but starts to widen during operation, notably well before the electrical device optimum is reached. Results from numerical simulations demonstrate that the only precondition for this event to occur is that the mobilities of anions (µ_a) and cations (µ_c) are not equal, and the direction of the EZ shift dictates µ_c > µ_a. Quantitative ion profiles reveal that the displacement of ions stops when the intrinsic zone stabilizes, confirming the relation between ion movement and EZ shift. Finally, simulations indicate that the experimental current peak for constant-voltage operation is intrinsic and the subsequent decay does not result from degradation, as commonly stated.