This work is focused on the study of the electromechanical response of fibrous materials produced by means of electrospinning. Such structures are considered an emerging technology for energy harvesting. In particular, PVdF-TrFe co-polymer nanofibers were electrospun and subjected to mechanical vibrations produced by an eccentric shaft. Experimental results showed that the specific electric response to mechanical vibrations, in the frequency range from 15 Hz to 37 Hz, is very high. Moreover, frequency response well follows the vibration source. Cost reduction and a simpler manufacturing technique represent other advantages of the electrospinning process compared to conventional production technologies.