Vertically aligned piezoelectric P(VDF-TrFE) nanotube array comprising nanotubes embedded in anodized alumina membrane matrix without entanglement has been fabricated. It is found that the crystallographic polar axes of the P(VDF-TrFE) nanotubes are oriented along the nanotubes long axes. Such a desired crystal orientation is due to the kinetic selection mechanism for lamellae growth confined in the nanopores. The preferred crystal orientation in nanotubes leads to huge piezoelectric coefficients of the P(VDF-TrFE). The piezoelectric strain and voltage coefficients of P(VDF-TrFE) nanotube array are observed to be 1.97 and 3.40 times of those for conventional spin coated film. Such a significant performance enhancement is attributed to the well-controlled polarization orientation, the elimination of the substrate constraint, and the low dielectric constant of the nanotube array. The P(VDF-TrFE) nanotube array exhibiting the unique structure and outstanding piezoelectric performance is promising for wide applications, including various electrical devices and electromechanical sensors and transducers.