Silicon anodes are promising for high-energy-density lithium-ion batteries. Nevertheless, unsatisfied initial Coulombic efficiency (ICE) and structure collapse are two barriers still hindering their application. Here, we report a 5 at.%-vanadium hybriding strategy to stabilize Si film anode, which delivers a high initial Coulombic efficiency of 92.1% with a discharge capacity of 2434.9 mAh·g⁻¹ and a desirable capacity retention of 80% after 100 cycles at 1 A·g⁻¹. Physical and electrochemical analyses demonstrate the Li_xPO_yF_z-rich inorganic solid-electrolyte interphase (SEI) and the low film internal strain are two advantageous factors for the desirable Li-ion storage reversibility and stability. A full battery with a LiFePO₄ cathode delivers the energy densities of 291.9 and 194.6 Wh·kg⁻¹ under power densities of 145.9 and 389.2 W·kg⁻¹, respectively. This result on Si anodes may pave the way to next-generation high-energy-density lithium-ion batteries.