The　low　intrinsic　electrical　conductivity,　low　specific　capacity,　and　high　solubility　of　organic　electrode　materials　have　significantly　plagued　its　practical　application　in　electrochemical　energy　storage　systems.　Herein,　bipolar　organic　molecules　combining　porphyrin　and　thiophene　functional　groups,　[5,　15-bis-(ethynyl)-10,　20-dithienylporphinato]M(II),　(M=　Cu,　Zn,　Co,　and　2H)　are　proposed　as　new　cathodes.　Thiophene　groups　and　nitrogen　atoms　act　as　active　sites　affording　8　electrons　transfer　during　redox　reaction　which　strongly　interact　with　both　cations　(Li+)　and　anions　(PF6−),　enabling　high　charge　storage　capability　and　fast　kinetic.　When　CuDETP　is　used　in　organic　lithium　batteries,　it　delivers　a　reversible　capacity　of　350　mAh　g　−　1　at　100　mA　g　−　1　and　a　high　specific　energy　density　of　773.6　Wh　kg−1　(based　on　the　cathode　material).　Meanwhile,　extremely　stable　cyclability　up　to　9000　cycles　is　achieved　owing　to　the　self-polymerziation　during　initial　charging　process.　This　investigation　has　great　enlightenment　for　the　molecular　design　and　application　of　organic　electrodes　in　terms　of　both　high　energy　densities　and　long　cycling　life.　©　2022　Elsevier　B.V.