Energy harvesting technology that can increase the operation time and decrease the device size is urgently needed in wireless electronics, portable devices, and implantable biosensors. This paper reports the experimental study of electromechanical coupling of PZT (piezoelectric) nanofiber composites which have the potential to be used for energy harvesting. The recorded voltage output was about 6 mV in the experiments. In this paper, we will describe the fabrication of the piezoelectric nanocomposites and demonstrate the characteristics of electro-mechanical coupling using a dynamic mechanical test. The piezoelectric nanocomposite assembly could produce high voltage and power output to be used as a power source, which might be used for wireless sensors, personal electronics, implantable bio-sensors, and bio-actuators.