In　this　paper,　gallium　nitride　(GaN)　nanoparticles　is　synthesized　on　the　nitrogen-doped　graphene　(NG)　(GaN@NG).　X-ray　absorption　fine　structure　(XAFS)　shows　the　distinct　interfacial　interaction　(Ga–N/N[sbnd]C).　This　well-designed　GaN@NG　shows　good　reversible　capacity　(793.2　mAh/g　at　0.1　A/g)　and　cycling　durability　with　98.5　%　capacity　retention　at　2.0　A/g　after　2000　cycles.　Both　DFT　analysis　and　electrochemical　kinetic　analysis　reveal　that　the　configuration　of　intriguing　electron　and　ion　bridges　is　able　to　control　and　tailor　the　interfacial　interaction　via　the　interfacial　coupled　chemical　bonds　in　GaN@NG　heterojunction.　Such　electron/ion　bridges　can　enhance　the　interfacial　charge　transfer　kinetics　and　prevent　pulverization/aggregation　via　the　ion/electron　channel　during　the　cycling.　As　expected,　the　lithium-ion　full　cell　(LiFePO4/C//GaN@NG)　exhibits　impressive　energy　and　power　densities　and　maintains　superior　cycling　stability.　This　electron/ion　bridges-related　structural　engineering　strategy　can　open　opportunities　for　the　traditional　electrode　material　to　achieve　the　high-performance　lithium　ion　storage　and　beyond.　©　2022　Elsevier　B.V.