An ongoing challenge with lithium-oxygen (Li-O-2) batteries is in deciphering the oxygen evolution reaction (OER) process related to the slow decomposition of the insulating lithium peroxide (Li2O2). Herein, we shed light on the behavior of Li2O2 oxidation by exploiting various in situ imaging, gas analysis, and electrochemical methods. At the low potentials 3.2-3.7 V (vs Li/Li+), OER is exclusive to the thinner parts of the Li2O2 deposits, which leads to O-2 gas evolution, followed by the concomitant release of superoxide species. At higher potentials, OER initiates at the sidewalls of the thicker Li2O2. The succeeding lateral decomposition of Li2O2 indicates the preferential Li+ and charge transport occurring at the sidewalls of Li2O2. To ameliorate the OER rate, we also investigate an alternative approach of rerouting charge carriers by using soluble redox mediators. Our in situ probes provide insights into the favorable charge-transport routes that can aid in promoting Li2O2 decomposition.