Unsatisfied initial Coulombic efficiency (ICE) and structure collapse are two problems still hindering the practical applications of silicon anodes. Hybriding Si with other metallic components can effectively improve the structural stability but is still not suitable to achieve high ICE. A high proportion of hybrid metallic components is essential for desired structural stability, yet it severely impairs the reversibility of lithiation and delithiation. Here, a 5 at%-vanadium hybriding strategy to stabilize Si film anode to deliver 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 analysis demonstrates the Li_xPO_yF_z-rich inorganic SEI and the low film internal strain are two advantageous factors for the desirable Li-ion storage reversibility and stability.