Zn(1-x)V(x)O (x = 0.015, 0.02, 0.025, 0.03, V -ZnO) nanofibers were synthesized by electrospinning, and a butterfly-shaped piezoelectric response was measured by scanning force microscopy. The diameters of V -ZnO nanofibers with hexagonal wurtzite phase are in the range of 50-300 nm. The large piezoelectric coefficient d(33) of 121 pm V(-1) was obtained and the high piezoelectric property may be attributed to the switchable spontaneous polarization induced by V dopants and the easier rotation of V-O bonds under an electric field. The result shows that the V-ZnO nanofiber is a promising candidate for nanoscale piezoelectric devices.