we demonstrated smart protective web consisted of nanosized beta phase polyvinylidene fluoride (PVDF) fibers with ferroelectricity on copper (Cu) foil to suppress Li dendrite. The beta phase PVDF fiber provides a well-ordered molecular structure, which ensures rapid Li-ion migration along PVDF fiber. That guarantee homogeneous Li-ions flux on the Cu current collector, leading to smooth Li surface occurs during Li deposition. In addition, the fiber could physically inhibit Li dendrite formation, resulting in no short-circuit and Li dead particle formation. Thus, the electrode consisted of PVDF fiber forms dense Li film during deposition, achieving high volume metric energy density (1937 mAh cm^-3). In full cell (LFP||PVDF electrode (PVDF web on Cu current collector), the electrode exhibits an excellent cycle performance (over 300 cycles) using conventional carbonate electrolytes at a current density of 1C.