The　search　for　high-performance　electrode　materials　in　organic　rechargeable　batteries　remains　a　key　challenge.　Reported　herein　is　a　molecular　structural　modification　of　perylene　imides,　a　promising　class　of　redox-active　electrode　materials,　for　improved　battery　performance.　The　Diels–Alder　extension　of　perylene　imides　at　the　lateral　position　led　to　the　simultaneous　incorporation　of　two　electron-withdrawing　carbonyl　groups　and　extension　of　the　π　system,　which　is　supposed　to　favor　high　specific　capacity,　operating　voltage,　and　electronic　conductivity.　After　the　chiral　dimerization　of　the　extended　species　with　1,2-diaminocyclohexane,　it　was　anticipated　that　the　porosity　and　coulombic　interactions　with　lithium　ions　would　be　promoted,　which　would　be　beneficial　for　fast　reaction　kinetics　and　long　cycling　life.　As　expected,　in　lithium　batteries,　the　obtained　chiral　and　π-extended　tweezer,　which　features　six　imide　groups　and　a　porous　solid-state　network　of　42.2　%　accessible　cell　volume,　was　found　to　deliver　a　reversible　capacity　of　92.1　mA　h　g−1　at　a　charge/discharge　rate　of　1　C　within　an　operating　voltage　window　of　1.60–2.80　V　versus　Li+/Li,　around　75　and　50　%　of　which　was　maintained　after　100　and　300　galvanostatic　cycles,　respectively,　much　better　than　those　of　unmodified　species.　©　2017　Wiley-VCH　Verlag　GmbH　&　Co.　KGaA,　Weinheim