The effect of stretching conditions, such as stretching ratios, temperatures and rates of extension, on the relative fraction of β-phase and electron structure as well as dielectric properties of poly(vinylidene fluoride) (PVDF) films was investigated. The fraction of β-phase in PVDF film increases greatly and reaches the peak of 93% after uniaxial stretching. Meanwhile, stretched spherulites and micro-strips paralleling with the stretching direction were observed in the matrix by atomic force microscopy (AFM). The results of fine structure of fluorine and carbon elements in PVDF, identified by X-ray absorption near edge structure (XANES), indicate that the coordination between F and H atoms of the adjacent chains is produced and thus enhances the dielectric response of the stretched film. As a result, the dielectric constant of the stretched film increases by 50% and achieves up to 12.1, as well as the dielectric loss being as low as 0.02.