In this study, we firstly propose an optical approach to investigate the ion profile of organic films in light-emitting electrochemical cells (LECs) without any invasive sputtering processes. In contrast to previous literatures, this pure optical strategy allows us to record clear and non-destructive ion profile images in the (Ru(dtb-bpy)3(PF6)2) consisted organic layer without interferences of complex collisions from the bombardment of secondary sputter induced ions in a conventional time-of-flight secondary ion mass spectrometry. By using the advanced position sensitive detector (PSD)-based Nanoscale Confocal Microscope, ion distribution profiles were successfully acquired based on the observation of nanoscale optical path length difference by measuring the refractive-index variation while the thickness of the LEC layer was fixed. Dynamic time-dependent ion profile displayed clear ion migration process under a 100 V applied bias at two ends of the LEC. This technique opens up a new avenue towards the future investigations of ion distributions inside organic/inorganic materials, Li-ion batteries, or micro-fluid channels without damaging the materials or disturbing the device operation.