Boosting　the　application　of　sodium-ion　batteries　(SIBs)　requires　the　development　of　economical　and　high-performance　anode　materials.　Here,　we　report　a　low-cost,　environmentally　friendly,　and　scalable　preparation　method　to　prepare　hard　carbon　(HC)　from　a　corn　starch　precursor　by　bioenzymatic　action.　This　strategy　can　effectively　inhibit　the　serious　foaming　of　starch　during　pretreatment　and　make　the　internal　microstructure　of　HC　have　a　larger　interlayer　distance,　a　more　disordered　structure,　and　higher　C═O　content.　As　an　anode　for　SIB,　the　enzymatic-assisted　synthesis　of　HC　has　a　high　reversible　capacity　of　346　mAh·g-1,　an　initial　Coulombic　efficiency　(ICE)　of　up　to　91%,　and　a　remarkably　enhanced　sodium-ion　transport　kinetics　of　271　mAh·g-1　at　5C.　Moreover,　it　displays　extremely　high　retention　of　92%　after　2500　cycles　at　1C　and　93%　after　6500　cycles　at　3C.　Such　HC　reaches　all　of　the　performance　indicators　for　anode　materials　as　well　as　a　low　surface　area,　demonstrating　the　advancement　of　this　synthetic　strategy　in　fabricating　practical　HC.　In　addition,　the　full-cell,　by　coupling　with　a　Na3V2(PO4)3　(NVP)　cathode,　delivers　a　high　capacity　of　323　mAh·g-1　at　1C　from　the　anode　side,　an　outstanding　rate　capability　of　313　mAh·g-1　at　5C,　and　good　cycling　performance.　These　satisfactory　electrochemical　properties,　combined　with　renewable　resources　and　scalable　synthesis　routes,　enable　the　present　HC　to　become　a　practical　SIB　anode.　©　2023　American　Chemical　Society.