Polyvinylidene fluoride (PVDF) nanofiber mats have played a significant role in wearable electronic devices that have been in great demand in recent decades. Although manifold PVDFbased freely stacked or well-aligned nanofiber mats created via the electrospinning process have been demonstrated to achieve multisensory capabilities with high sensitivity and long detection range, rarely have any of them proved their ability with a stable process and accurate processing parameters. In this work, we successfully developed freely stacked and well-aligned PVDF nanofiber mats with diameters ranging from micrometers to nanometers, providing stable performance for wearable electronic devices. Through in-depth investigations into material preparation, electrospinning, and fiber collection processes, we revealed the relationship between the nanofiber morphology, β-phase fraction, and piezoelectric output with various process parameters. Characterized by analytical methods, we have established a mature, reliable nanofiber mat fabrication system capable of mass-producing PVDF nanofibers with the required diameter and consistent properties. At 18 kV voltage and 60% RH humidity, the uniformity of the fiber diameter and β-phase content was maintained in a favorable range. When the drum speed increased to 2000 r/s, the fiber orientation and β-phase content increased. We assembled aligned PVDF nanofiber mats with conductive fabric in a flexible piezoelectric sensor that successfully monitored different body movements and produced an output voltage of 0.1 V. This study provides the necessary process parameters for the large-scale production of high-quality PVDF nanofiber mats and provides clear guidance for beginners in the field of nanofiber mat manufacturing.