In the last decade, numerous physical modification methods have been introduced to enhance triboelectric nanogenerator (TENG) performance although they generally require complex and multiple fabrication processes. This study proposes a facile fabrication process for Poly(vinylidene fluoride) (PVDF) nanofiber (NF) mats incorporating additive and nonadditive physical modifications. Patterned PVDF NF mats are prepared by electrospinning using a metal mesh as the NF collector. As a negative triboelectric material, the TENG with the patterned PVDF NF mat exhibits superior performance owing to the engineered morphology of the contact layer. PVDF is crucial in TENGs owing to its superior ferroelectric properties and surface charge density when combined with specific electroceramics. Hence, the synergy of the physical modification methods is achieved by incorporating BaTiO3 (BTO) nanoparticles (NPs) into the PVDF. By functionalizing BTO NPs with polydopamine, the TENG performance is further improved owing to the enhanced dispersion of NPs and improved crystallinity of the PVDF chains. Utilizing large NPs produces a nanopatterning effect on the NF surface, thereby resulting in the hierarchical structure of the NF mats. The source of the voltage signals from the TENG is analyzed using fast Fourier transform.