Organic materials for Li-ion battery application continue gaining attention due the virtue of low cost, environmental benignity, and so on. A new class of electroactive organic material called polyimides is particularly important due to the extra stability exhibited at higher current rates. High-performance rechargeable lithium battery cathodes based on polyimides of 3,4,9,10-perylenetetracarboxylicacid-dianhydride are prepared. The novel electrodes exhibit good rate capability and improved cycling stability, which result from their combined beneficial properties such as the presence of additional carbonyl groups, favorable band gap, and enhanced conductivity, making it a potential material for greener and sustainable electrochemical storage devices.