Poly(vinylidene fluoride)(PVDF), a fluoropolymer, is one of the characteristic polymer materials with excellent electrical properties. Depending on different processing conditions, PVDF can form into non-polar crystalline as α-phase and polar crystalline as β-, γ- and δ- phases. From the industrial application, β-phase is the most attractive phase of PVDF. It is because that β-phase shows the largest polarization due to all-trans planar zigzag conformation. β-phase could perform ferroelectric, piezoelectric, and pyroelectric properties. Generally, β-PVDF can be obtained from stretching PVDF with α-phase. In this work, we performed rolling process in order to induce phase transition from the α-phase to the β-phase. We also used pressing process and stretching process as different deformations to compare with the rolling process. Moreover, we investigated the structural changes between the specimens before and after the film rolling process by FT-IR and WAXD.