The interplay between ionic and electronic charge carriers in mixed conductors offers rich physics and unique device potential. In light-emitting electrochemical cells (LEECs), for example, the redistribution of ions assists the injection of electronic carriers and leads to efficient light emission. The mechanism of operation of LEECs has been controversial, as there is no consensus regarding the distribution of electric field in these devices. Here, we probe the operation of LEECs using electric force microscopy on planar devices. We show that obtaining the appropriate boundary conditions is essential for capturing the underlying device physics. A patterning scheme that avoids overlap between the mixed-conductor layer and the metal electrodes enabled the accurate in situ measurement of the electric-field distribution. The results show that accumulation and depletion of mobile ions near the electrodes create high interfacial electric fields that enhance the injection of electronic carriers.