Wearable piezoelectric nanogenerators (PENGs) are increasingly significant in healthcare and energy harvesting applications due to their ability to convert mechanical energy into electrical signals. In this study, we developed PENGs by incorporating crab shell powder (CS-NFs) into electrospun polyvinylidene fluoride (PVDF) nanofibers to enhance their piezoelectric properties. The PVDF-CS-NFs (PC-NFs) composites were evaluated for structural, thermal, and piezoelectric performance. The 1.5 wt% CS-NFs composite exhibited a notable improvement, with a maximum output voltage of 19 V under mechanical deformation, significantly higher than pristine PVDF NFs. Furthermore, the device demonstrated excellent sensitivity in real-time respiratory monitoring when applied to various body locations, including the chest, throat, and mask. Additionally, the PC-NFs-based PENGs were capable of charging a 2.2 µF capacitor to 2 V within 180 s and powering 56 LEDs. These results underscore the potential of using sustainable crab shell waste in biocompatible, eco-friendly piezoelectric devices for wearable sensors and energy harvesting applications.