To understand the deterioration of cycle performance and energy efficiency related with non-aqueous rechargeable Li–air batteries, a micro–macro homogeneous model has been developed to include the practical feature of Li2CO3 formation which occurs by electrolyte degradation during battery cycling. The discharge products can limit the cyclability and passivate the porous-cathode surface. A modelling study of cycling behaviour and cell performance for Li–air batteries in a non-aqueous electrolyte is presented which includes the influence of electrolyte solution degradation. The cycle performance deterioration measured in term of retention of discharge capacity on cycling was predicted from the developed model which includes the effect of irreversible Li2CO3 discharge product. A good agreement between this cell cycling simulation and porous-electrode experiment data is obtained, thus creating a more reliable model for a rechargeable Li–air battery in non-aqueous electrolyte. The cell cycling simulation and porous-electrode experiment indicate that there has been gradual decrease for retention of discharge capacity in a number of battery cycles due to the effect of irreversible formation of the Li2CO3 discharge product. The termination of the cell discharge is not from the pore blockage by the repeated depositing of discharge products as there are some available pores at the end of each discharge cycle.