Piezoelectric materials capable of converting between mechanical and electrical energy have a great range of potential applications in micro- and nano-scale smart devices; however, their performance tends to be greatly degraded when reduced to a thin film due to the large clamping force by the substrate and surrounding materials. Herein, we report an effective method for synthesizing isolated piezoelectric nano-materials as means to relax the clamping force and recover original piezoelectric properties of the materials. Using this, environmentally friendly single-crystalline NaxK1-xNbO3 (NKN) piezoelectric nano-rod arrays were successfully synthesized by conventional pulsed-laser deposition and demonstrated to have a remarkably enhanced piezoelectric performance. The shape of the nano-structure was also found to be easily manipulated by varying the energy conditions of the physical vapor. We anticipate that this work will provide a way to produce piezoelectric micro- and nano-devices suitable for practical application, and in doing so, open a new path for the development of complex metal-oxide nano-structures.