Self-powered operation, flexibility, excellent mechanical properties, and ultra-high sensitivity are highly desired properties for pressure sensors in human health monitoring and anthropomorphic robotic systems. Piezoelectric pressure sensors, with enhanced electromechanical performance to effectively distinguish multiple mechanical stimuli (including pressing, stretching, bending, and twisting), have attracted interest to precisely acquire the weak signals of the human body. In this work, we prepared a poly(vinylidene fluoride-trifluoroethylene)/ multi-walled carbon nanotube (P(VDF-TrFE)/MWCNT) composite by an electrospinning process and stretched it to achieve alignment of the polymer chains. The composite membrane demonstrated excellent piezoelectricy, favorable mechanical strength, and high sensitivity. The piezoelectric coefficient d 33 value was approximately 50 pm/V, the Young’s modulus was ~0.986 GPa, and the sensitivity was ~540 mV/N. The resulting composite membrane was employed as a piezoelectric pressure sensor to monitor small physiological signals including pulse, breath, and small motions of muscle and joints such as swallowing, chewing, and finger and wrist movements. Moderate doping with carbon nanotubes had a positive impact on the formation of the β phase of the piezoelectric device, and the piezoelectric pressure sensor has the potential for application in health care systems and smart wearable devices.