Flexible piezoelectric nanogenerators (PENGs) are promising candidates for clean energy harvesting and powering electronics, especially for low-power modules. In this study, a PENG has been fabricated by incorporating functionalized mono-/few-layered hexagonal boron nitride nanosheets (F-hBNNS) in a polyvinylidene fluoride (PVDF) polymeric matrix. The synthesized 2D nanosheets are well characterized using different spectroscopic and microscopic methods. The analysis showed successful exfoliation of hBN, which indicated less than three layers of hBN after exfoliation and sulfonated and carboxylated functionalization on the surface. Also, the piezoresponse force microscopy (PFM) tests revealed a 3 times higher piezoelectric coefficient for F-hBNNS compared to that of the non-functionalized hBN with the same number of layers. The synthesized F-hBNNS with piezo-flexoelectric properties boosted the energy harvesting performance of the electrospun PVDF-based fibrous mats 5.5 times. The open-circuit output voltage test showed 23 V at 4 Hz with a power density of 1.93 μW/cm2 at a resistance loading of 16 MΩ in a simple finger tapping. The fabricated PENGs showed no decline in voltage output over 1000 cycles of bending-unbending of a robotic finger. It is proposed that the enhanced performance is due to (i) the synergistic effects of the flexoelectric and piezoelectric properties of synthesized F-hBNNS in the PVDF matrix and (ii) the manipulation of the crystalline structure of the PVDF chains, which is increased to 90% β-phase crystallinity with 49.03% total degree of crystallinity. This study shows the compatibility of the fabricated PENGs with the human body's biomechanics for being used as an efficient energy source for wearable devices with low power consumption.