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Abstract The electroactive β-phase in Poly (vinylidene fluoride, PVDF) is the most desirable conformation due to its highest pyro- and piezoelectric properties, which make it feasible to be used as flexible sensors, wearable electronics, and energy harvesters etc. In this study, we successfully developed a method to obtain high-content β-phase PVDF films and nanofiber meshes by mechanical stretching and electric spinning. The phase transition process and pyro- and piezoelectric effects of stretched films and nanofiber meshes were characterized by monitoring the polarized light microscopy (PLM) images, outputting currents and open-circuit voltages respectively, which were proved to be closely related to stretching ratio (λ) and concentrations. This study could expand a new route for the easy fabrication and wide application of PVDF films or fibers in wearable electronics, sensors, and energy harvesting devices.