This paper discusses an in-depth experimental study on the fretting wear behavior of PVDF (polyvinylidene fluoride) piezoelectric thin film against a Si3N4 ceramic sphere under air conditions. A fretting wear device with a ball-on-plate contact configuration was applied. The changes of displacement amplitude, normal force, and applied voltage were taken into account. The friction logs were used to determine the contact state of the PVDF thin film during the fretting test. The 3D topography instrument and scanning electron microscope (SEM) were used to measure the details of the surface morphology and wear volume. The test results of PVDF thin films under different normal force, displacement amplitude, and applied voltage are summarized through the collection and analysis of experimental data. It is shown that the creep and plastic deformation lead to obvious winkles at the contact surface, which may decrease the specific wear rate of PVDF thin films.