Li3BN2 is investigated for the first time as a transition metal free, high capacity cathode material for Li-ion batteries. It is shown that α-Li3BN2 can exhibit a specific capacity of 890 mA h g−1 with the charge storage mechanism associated with the valence state change of N ions in the BN2 anion. The specific capacity demonstrated in this study is the highest one ever reported in literature for an intercalation-type cathode material. Further, using the valence state change of N ions as a charge storage mechanism opens the door for designing additional high performance, transition metal free electrodes in the future.