The crystallinities of Ag-doped poly(vinylidene fluoride) (PVDF) films were modified by removing Ag⁺ using a novel washing process, which allowed control of the ratio of γ- and β-phases. The polarity of the composite film without Ag⁺ removal through the washing process reached 98%, and the β-phase content in the total electroactive phase was increased to 61%, according to Fourier-transform infrared spectroscopy. When Ag⁺ were removed through a process involving several cycles of washing, filtering, drying, and re-dissolving, the highest ratio of the γ-phase was increased to 67%, 28% higher than that before washing. This showed that Ag⁺ induced β-phase formation while Ag nanoparticles induced γ-phase formation, and that the ratio of γ- and β-phases in PVDF composite films can be controlled to suit specific applications by this washing process.