This work reports the transition from rectifying type to resistive switching in semicrystalline, unpoled intrinsic form of polyvinylidene fluoride (PVDF) thin films in Ag/PVDF/Au capacitor-like structures. The transition is noted after the breakdown of Schottky barrier at electric fields of 3 MV/cm along with the changeover from asymmetric to symmetric I-V curves. The sharp change from asymmetric to symmetric I-V loops further revealed bipolar-resistive switching. The asymmetric and symmetric I-V transport mechanisms are evaluated with the Fowler-Nordheim tunneling and space-charge-limited current mechanisms at high voltages. Furthermore, the resistive-switching phenomena are attributed to the filament formation from the ohmic response of the low-resistance state.