Electrochemical lithiation/delithiation studies are carried out on three different aromatic diimide lithium carboxylates. Among all, naphthalene diimide based dilithium carboxylate delivers a remarkably stable capacity of 134mAhg⿿1 at 2.24V vs. Li/Li+ over 125 cycles with a low polarization of 50mV. A striking feature is that, the lithiation/delithiation process is biphasic with excellent plateau behaviour in the voltage-composition profile. DFT calculations confirm the lower band gap and higher electron affinity for this compound.