Architecting　grain　crystallographic　orientation　can　modulate　charge　distribution　and　chemomechanical　properties　for　enhancing　the　performance　of　polycrystalline　battery　materials.　However,　probing　the　interplay　between　charge　distribution,　grain　crystallographic　orientation,　and　performance　remains　a　daunting　challenge.　Herein,　we　elucidate　the　spatially　resolved　charge　distribution　in　lithium　layered　oxides　with　different　grain　crystallographic　arrangements　and　establish　a　model　to　quantify　their　charge　distributions.　While　the　holistic　＂surface-to-bulk＂　charge　distribution　prevails　in　polycrystalline　particles,　the　crystallographic　orientation-guided　redox　reaction　governs　the　charge　distribution　in　the　local　charged　nanodomains.　Compared　to　the　randomly　oriented　grains,　the　radially　aligned　grains　exhibit　a　lower　cell　polarization　and　higher　capacity　retention　upon　battery　cycling.　The　radially　aligned　grains　create　less　tortuous　lithium　ion　pathways,　thus　improving　the　charge　homogeneity　as　statistically　quantified　from　over　20　million　nanodomains　in　polycrystalline　particles.　This　study　provides　an　improved　understanding　of　the　charge　distribution　and　chemomechanical　properties　of　polycrystalline　battery　materials.