Lithium-ion　batteries　(LIBs)　have　been　widely　used　as　grid-level　energy　storage　systems　to　power　electric　vehicles,　hybrid　electric　vehicles,　and　portable　electronic　devices.　However,　it　is　a　big　challenge　to　develop　high-capacity　electrode　materials　with　large　energy　storage　and　ultrafast　charging　capability　simultaneously　due　to　the　sluggish　charge　carrier　transport　in　bulk　materials　and　fragments　of　active　materials.　To　address　this　issue,　composite　electrodes　of　SnO2　nanodots　and　Sn　nanoclusters　embedded　in　hollow　porous　carbon　nanofibers　(denoted　as　SnO2@HPCNFs　and　Sn@HPCNFs)　were　respectively　constructed　programmatically　for　customized　LIBs.　Highly　interconnected　carbon　nanofiber　networks　served　as　fast　electron　transport　pathways.　Additionally,　the　hierarchical　hollow　and　porous　structure　facilitated　rapid　Li-ion　diffusion　and　alleviated　the　volume　expansion　of　Sn　and　SnO2.　SnO2@HPCNFs　delivered　a　remarkably　high　capacity　of　899.3　mA　h　g−1　at　0.1　A　g−1　due　to　enhanced　Li　adsorption　and　high　ionic　diffusivity.　Meanwhile,　Sn@HPCNFs　displayed　fast　charging　capability　and　superior　high　rate　performance　of　238.8　mA　h　g−1　at　5　A　g−1　(∼10　C)　due　to　the　synergetic　effect　of　enhanced　Li-ion　storage　in　the　bulk　pores　of　Sn　and　improved　electronic　conductivity.　The　investigation　of　the　electrochemical　behaviors　of　SnO2　and　Sn　by　tailoring　the　carbonization　temperature　provides　new　insight　into　constructing　high-capacity　anode　materials　for　high-performance　energy　storage　devices.　©　2023,　Science　China　Press.