Bimetallic SbSn alloy stands out among the anode materials for sodium‐ion batteries (SIBs) because of its high theoretical specific capacity (752 mAh g−1) and good electrical conductivity. However, the major challenge is the large volume change during cycling processes, bringing about rapid capacity decay. Herein, to cope with this issue, through electrostatic spinning and high temperature calcination reduction, the unique bean pod‐like free‐standing membrane is designed initially, filling SbSn dots into integrated carbon matrix including hollow carbon spheres and nitrogen‐doped carbon fibers (B‐SbSn/NCFs). Significantly, the synergistic carbon matrix not only improves the conductivity and flexibility, but provides enough buffer space to alleviate the large volume change of metal particles. More importantly, the B‐SbSn/NCFs free‐standing membrane can be directly used as the anode without polymer binder and conductive agent, which improves the energy density and reaction kinetics. Satisfyingly, the free‐standing BSbSn/NCFs membrane anode shows excellent electrochemical performance in SIB. The specific capacity of the membrane electrode can maintain 486.9 mAh g−1 and the coulombic efficiency is close to 100% after 400 cycles at 100 mA g−1. Furthermore, the full cell based on B‐SbSn/NCFs anode also exhibits the good electrochemical performance.