Poly(vinylidene fluoride) (PVDF) has excellent pyro- and piezoelectric properties which are related to the β-crystal of PVDF. Most of the β-crystal of PVDF can be transformed from the α-crystal by mechanical stretching. The effects of stretching conditions on the transformation from α to β phase of PVDF were studied in this paper. In addition, changes of crystalline structure of PVDF during the stretching process were observed in situ under an optical tensile stress microscopy tester, and the samples after being stretched were investigated using a 3D digital microscope and an infrared microscope. The results show that stretching temperature (T_s) and drawing ratio (λ) are critical to the transformation from α-crystal to β-crystal of PVDF. The T_s around 100 °C and λ above 3 is recommended. The in situ observation indicates that the deformation of crystalline structure began from the middle of α-spherulite and extended to another spherulite, and caused the large-scale transformation. Scanning results of infrared microspectroscopic and 3D digital microscopy revealed that α phase of PVDF would change into β phase with the deformation of the spherulite, and the distribution of the different crystalline phase in PVDF after being stretched was also given. It is believed that this work is instructive and meaningful to studies on phase transformation and production of the piezoelectric film of PVDF.