Polymer　batteries　have　attracted　increasing　attention　because　of　their　advantages　of　good　flexibility,　high　compatibility　with　organic　electrolytes,　and　high　environmental　friendliness.　However,　the　low　utilization　rate　of　the　redox-active　units　buried　in　polymeric　network　and　the　slow　kinetics　of　the　electrochemical　reactions　hinder　their　development.　Herein,　mono-　and　diviologen　functionalities　are　attached　to　a　tetramethylbiphenol-derived　poly(arylene　ether　ketone)　(TPAEK)　by　postmodification　to　yield　two　redox-active　polymers　MV-TPAEK　and　2MV-TPAEK,　respectively,　and　polymer　electrodes　are　prepared　by　mixing　them　with　N-doped　carbon　nanotubes　without　binders.　When　paired　with　the　Li　counter　electrode,　the　MV-TPAEK　and　2MV-TPAEK　electrodes　deliver　specific　discharge　capacities　of　93.3　and　95.4　mA　h　g-1,　respectively,　at　a　current　rate　of　0.1　C　and　maintain　36.1　and　42.3　mA　h　g-1,　respectively,　after　100　galvanostatic　cycles.　When　the　current　rate　is　increased　to　10　C,　the　specific　discharge　capacities　are　lowered　to　13.9　and　25.8　mA　h　g-1,　respectively,　for　the　MV-TPAEK　and　2MV-TPAEK　electrodes　due　to　the　increased　electrochemical　polarizations.　All　of　these　results　prove　that　the　2MV-TPAEK　electrode　is　better　than　the　MV-TPAEK　electrode.　When　the　counter　electrode　is　changed　to　Na,　the　trend　remains　the　same.　Given　the　fact　that　the　two　polymers　have　an　identical　backbone,　the　improved　electrochemical　performance　of　2MV-TPAEK　may　be　ascribed　to　the　larger　mobility　of　the　extended　2MV　pendant,　which　is　beneficial　for　the　formation　of　more　molecular　voids　and　stacked　intermediate　structures　for　better　charge　transfer.　This　study　paves　the　way　for　the　molecular　design　of　redox-active　polymers　for　high-performance　polymer　batteries.　©　2023　American　Chemical　Society.