The demand for self-powered, flexible, and wearable electronic devices has been increasing in recent years for physiological and biomedical applications in real-time detection due to their higher flexibility and stretchability. This work fabricated a highly sensitive, self-powered wearable microdevice with Poly-Vinylidene Fluoride-Tetra Fluoroethylene (PVDF-TrFE) nano-fibers using an electrospinning technique. The dielectric response of the polymer was improved by incorporating the reduced-graphene-oxide (rGO) multi-walled carbon nano-tubes (MWCNTs) through doping. The dielectric behavior and piezoelectric effect were improved through the stretching and orientation of polymeric chains. The outermost layer was attained by chemical vapor deposition (CVD) of conductive polymer poly (3,4-ethylenedioxythiophene) to enhance the electrical conductivity and sensitivity. The hetero-structured nano-composite comprises PVDF-TrFE doped with rGO-MWCNTs over poly (3,4-ethylenedioxythiophene) (PEDOT), forming continuous self-assembly. The piezoelectric pressure sensor is capable of detecting human physiological vital signs. The pressure sensor exhibits a high-pressure sensitivity of 19.09 kPa−1, over a sensing range of 1.0 Pa to 25 kPa, and excellent cycling stability of 10,000 cycles. The study reveals that the piezoelectric pressure sensor has superior sensing performance and is capable of monitoring human vital signs, including heartbeat and wrist pulse, masticatory movement, voice recognition, and eye blinking signals. The research work demonstrates that the device could potentially eliminate metallic sensors and be used for early disease diagnosis in biomedical and personal healthcare applications.