Rechargeable　aqueous　aluminum　batteries　(AABs)　are　promising　energy　storage　technologies　owing　to　their　high　safety　and　ultra-high　energy-to-price　ratio.　However,　either　the　strong　electrostatic　forces　between　high-charge-density　Al3+　and　host　lattice,　or　sluggish　large　carrier-ion　diffusion　toward　the　conventional　inorganic　cathodes　generates　inferior　cycling　stability　and　low　rate-capacity.　To　overcome　these　inherent　confinements,　a　series　of　promising　redox-active　organic　materials　(ROMs)　are　investigated　and　a　pi-conjugated　structure　ROMs　with　synergistic　C=　O　and　C=　N　groups　is　optimized　as　the　new　cathode　in　AABs.　Benefiting　from　the　joint　utilization　of　multi-redox　centers　and　rich　pi-pi　intermolecular　interactions,　the　optimized　ROMs　with　unique　ion　coordination　storage　mechanism　facilely　accommodate　complex　active　ions　with　mitigated　coulombic　repulsion　and　robust　lattice　structure,　which　is　further　validated　via　theoretical　simulations.　Thus,　the　cathode　achieves　enhanced　rate　performance　(153.9　mAh　g(-1)　at　2.0　A　g(-1))　and　one　of　the　best　long-term　stabilities　(125.7　mAh　g(-1)　after　4,000　cycles　at　1.0　A　g(-1))　in　AABs.　Via　molecular　exploitation,　this　work　paves　the　new　direction　toward　high-performance　cathode　materials　in　aqueous　multivalent-ion　battery　systems.