Organic　redox-active　compounds　are　promising　alternatives　to　traditional　inorganic　counterparts　because　of　their　sustainable　resources　and　highly　tunable　properties.　However,　their　solubility　in　organic　electrolyte　solvents　and　the　sluggish　electrode　reactions　hinder　their　further　development.　Herein,　an　intrinsically　microporous　decabromopropyl　pillar[5]arene　(P5Br)　was　used　to　support　the　methyl　viologen　(MV)　functionality　to　yield　two　non-crosslinked　and　crosslinked　organic　electrode　materials,　namely　MV-P5Br　and　CMV-P5Br,　respectively.　When　evaluating　against　Li　metal　counter　electrode,　the　MV-P5Br　and　CMV-P5Br　electrodes　delivered　high　discharge　capacities　of　87.9　and　92.7　mAh　g−1　at　0.1　C,　respectively,　which　are　close　to　their　theoretical　values.　After　galvanostatic　cycling　at　0.1　C　for　100　cycles,　the　CMV-P5Br　electrode　maintained　a　discharge　capacity　of　82.3　mAh　g−1,　much　higher　than　the　43.7　mAh　g−1　of　the　MV-P5Br　electrode.　When　the　current　rate　was　increased　to　10　C,　the　CMV-P5Br　electrode　delivered　a　discharge　capacity　of　60.7　mAh　g−1,　also　higher　than　the　41.3　mAh　g−1　of　the　MV-P5Br　electrode.　The　increased　cycling　stability　and　rate　performance　of　the　CMV-P5Br　electrode　were　attributed　to　the　diminished　solubility　and　the　enhanced　ion　diffusion　coefficient　of　the　active　material.　When　the　counter　electrode　was　changed　to　Na　metal,　similar　results　were　obtained,　suggesting　that　the　CMV-P5Br　electrode　can　also　be　used　in　Na-ion　systems.　This　study　demonstrates　that　the　combination　of　crosslinked　and　microporous　structure　is　highly　effective　to　boost　the　electrochemical　performance　of　organic　redox-active　compounds　for　rechargeable　batteries.　©　2024　Elsevier　Ltd