Attracted by high energy density and power density, metal‐sulfides anodes have promising application prospects in fast charging batteries. However, they still suffer from low electrical conductivity and sluggish electrochemical kinetics, resulting in poor fast charging capacity. Herein, spindle‐like antimony sulfide (Sb2S3) is rationally tailored with favorable (hk1) crystal orientation and rich S‐vacancies using a simple hydrothermal method, which improve electric conductivity significantly. Triggered by S‐vacancies lattice defects, SbOC interfacial bonds and S‐doped carbon layer are built successfully. Under their multiple‐controlling synergistic effects, electrochemical kinetics and reaction reversibility are promoted effectively. As expected, Sb2S3/HTAB@C show high average initial coulombic efficiency of 86.12%, and deliver 624.5 and 428.4 mAh g−1 after cycling 100 cycles at 10.0 and 30.0 A g−1 respectively in Li‐ion batteries (LIBs). Electrochemical kinetic analysis and theoretical calculations indicate that superior ultrafast charging capacity originates from quickened interfacial electron/ions transferring and alleviates electrochemical polarization. Ex situ technologies powerfully prove good stability of (hk1) orientation, SbOC bonds and S‐doped carbon layer. Notably, full LIBs of SS/H@C versus LiFePO4@C display 500.9 and 398.3 mAh g−1 at 5.0 and 10.0 A g−1, respectively. This study is anticipated to open avenue to develop advanced metal‐sulfides anodes for fast charging batteries.