Construction　of　ordered　structures　that　respond　rapidly　to　environmental　stimuli　has　fascinating　possibilities　for　utilization　in　energy　storage,　wearable　electronics,　and　biotechnology.　Silicon/carbon　(Si/C)　anodes　with　extremely　high　energy　densities　have　sparked　widespread　interest　for　lithium-ion　batteries　(LIBs),　while　their　implementation　is　constrained　via　mechanical　structure　deterioration,　continued　growth　of　the　solid　electrolyte　interface　(SEI),　and　cycling　instability.　In　this　study,　a　piezoelectric　Bi0.5Na0.5TiO3　(BNT)　layer　is　facilely　deposited　onto　Si/C@CNTs　anodes　to　drive　piezoelectric　fields　upon　large　volume　expansion　of　Si/C@CNTs　electrode　materials,　resulting　in　the　modulation　of　interfacial　Li+　kinetics　during　cycling　and　providing　an　electrochemical　reaction　with　a　mechanically　robust　and　chemically　stable　substrate.　In-depth　investigations　into　theoretical　computation,　multi-scale　in/ex　situ　characterizations,　and　finite　element　analysis　reveal　that　the　improved　structural　stability,　suppressed　volume　variations,　and　controlled　ion　transportation　are　responsible　for　the　improvement　mechanism　of　BNT　decorating.　These　discoveries　provide　insight　into　the　surface　coupling　technique　between　mechanical　and　electric　fields　to　control　the　interfacial　Li+　kinetics　behavior　and　improve　structural　stability　for　alloy-based　anodes,　which　will　also　spark　a　great　deal　attention　from　researchers　and　technologists　in　multifunctional　surface　engineering　for　electrochemical　systems.　©　2023　The　Authors.　Advanced　Science　published　by　Wiley-VCH　GmbH.