Lead-free (Na0.5Bi0.5)(0.94)TiO3-Ba0.06TiO3 (NBT-BT6) nanofibers were synthesized by the sol-gel process and electro-spinning, and a butterfly-shaped piezoelectric response was measured by scanning force microscopy. NBT-BT6 nanofibers with perovskite phase were formed, after being cleaned at 700 degrees C for 1 hour, and the diameters are in the range of 150 nm to 300 nm. The average value of the effective piezoelectric coefficient d(33) is 102 pm/V The high piezoelectricity may be attributed to the easiness for the electric field to tilt the polar vector of the domain and to the increase of the possible spontaneous polarization direction. There is a potential for the application of NBT-BT6 nanofibers in nanoscale piezoelectric devices. (C) 2009 WILEY-VCH Verlag GmbH & Co KGaA, Weinheim