In the field of energy storage devices the pursuit for cheap, high energy density, reliable secondary batteries is at the top of the agenda. The Li−O2 battery is one of the possible technologies that, in theory, should be able to close the gap, which exists between the present state-of-the-art Liion technologies and the demand placed on batteries by technologies such as electrical vehicles. Here we present a redox probing study of the charge transfer across the main deposition product lithium peroxide, Li2O2, in the Li−O2 battery using outer-sphere redox shuttles. The change in heterogeneous electron transfer exchange rate as a function of the potential and the Li2O2 layer thickness (∼depth-of-discharge) was determined using electrochemical impedance spectroscopy. The attenuation of the electron transfer exchange rate with film thickness is dependent on the probing potential, providing evidence that hole transport is the dominant process for charge transfer through Li2O2 and showing that the origin of the sudden death observed upon discharge is due to charge transport limitations.