In this work, we have studied the electronic structure of different Li 2 O 2 surfaces using the hybrid functional HSE that is capable of adequately describing the electronic structure and modeling the localization of hole polarons. The insulating nature of the all studied surfaces has been confirmed. In the non-stoichiometric terminations with low-coordinated surface oxygen atoms, we have also confirmed a similar charge self-trapping behaviour as found in Li 2 O 2 bulk. Then, we have examined the Li 2 O 2 decomposition that occurs during the recharge process using HSE to take into account the presence of the surface polarons in the electrochemical intermediate steps. These results have been compared with the ones obtained using the GGA functional, which tend to delocalize the excess of charge carriers.