High discharged energy density observed in poly(vinylidene fluoride) (PVDF) based copolymers has attracted considerable research interests in the past years. Crystalline properties exhibit great influence on their dielectric and energy storage properties. To understand how crystalline properties influence the energy storage properties of PVDF, PVDF films with three different crystal forms are investigated in this paper. It is shown that γ-PVDF is allowed to work under higher electric fields than α- and β-PVDF in the absence of phase transition in α-PVDF and early polarization saturation in β-PVDF. Consequently, γ-PVDF exhibits the highest energy density of 14 J/cm3 under 500 MV/m electric field.