Recently, piezoelectric nanogenerators have received great interest as they can convert waste mechanical and radiative energy to electricity and can be used in self‐energy generating systems and sensor technologies. In this study, electrospun poly(vinylidene fluoride) (PVDF) nanofiber‐based piezoelectric nanogenerators with reduced graphene oxide (rGO), polyaniline (PANI), and PANI‐functionalized rGO (rGOPANI) have been developed. Two different types of nanofiber mats were produced: First, rGO‐ and rGOPANI‐doped PVDF nanofiber mats and second, rGO, PANI and rGOPANI‐spray‐coated PVDF nanofiber mats that have worked as nanogenerators' electrodes. Then, characterizations of samples were performed in terms of piezoelectricity, Fourier transform infrared (FTIR) spectrophotometric, X‐ray diffractions (XRD), and scanning electron microscopy analyses. FTIR and XRD results confirmed that piezoelectric β‐crystalline phase of PVDF occurred after the electrospinning process. Besides, maximum output voltages were obtained as 7.84 and 10.60 V for rGO‐doped PVDF and rGOPANI‐coated PVDF nanofiber mats, respectively. As a result, the doped nanofibers were found to be more successful due to the higher device accuracy in sensor technologies compared with spray‐coated samples. However, spray‐coating method proved to be more suitable technique for the production of nanogenerators on an industrial scale in terms of fast and large‐scale applicability. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 137, 48517. [ABSTRACT FROM AUTHOR]