The mechanisms and efficiency of charge transport in lithium peroxide (Li₂O₂) are key factors in understanding the performance of non-aqueous Li–air batteries. Towards revealing these mechanisms, here we use first-principles calculations to predict the concentrations and mobilities of charge carriers and intrinsic defects in Li₂O₂ as a function of cell voltage. Our calculations reveal that changes in the charge state of O₂ dimers controls the defect chemistry and conductivity of Li₂O₂. Negative lithium vacancies (missing Li⁺) and small hole polarons are identified as the dominant charge carriers. The electronic conductivity associated with polaron hopping (5 × 10⁻²⁰ S cm⁻¹) is comparable to the ionic conductivity arising from the migration of Li-ions (4 × 10⁻¹⁹ S cm⁻¹), suggesting that charge transport in Li₂O₂ occurs through a mixture of ionic and polaronic contributions. These data indicate that the bulk regions of crystalline Li₂O₂ are insulating, with appreciable charge transport occurring only at moderately high charging potentials that drive partial delithiation. The implications of limited charge transport on discharge and recharge mechanisms are discussed, and a two-stage charging process linking charge transport, discharge product morphology, and overpotentials is described. We conclude that achieving both high discharge capacities and efficient charging will depend upon access to alternative mechanisms that bypass bulk charge transport. More generally, we describe how the presence of a species that can change charge state – e.g., O₂ dimers in alkaline metal-based peroxides – may impact rechargeability in metal–air batteries.