Phase transformations of [001], [110], and [111] oriented Pb(Zn 1/3Nb2/3)O3-6%PbTiO3 (PZN-6%PT) single crystals have been investigated by means of dielectric permittivity and loss, x-ray diffraction and depolarization current as function of temperature (from 250 to 500 K). The unpoled samples undergo R-T-C phase transition sequence during zero field heating (ZFH), where R, T, and C are rhombohedral, tetragonal, and cubic phases, respectively. Under electric field (0.5 kV/cm), an intermediate orthorhombic (O) phase is induced between the T and R phases in the field cooling (FC) process. This phase reappears during subsequent zero field heating of the poled sample (zero field heating after field cooling ZFHaFC). The existence range of this O phase depends on both the crystal orientation and the measurement conditions (FC or ZFHaFC). Finally, for the [001] direction, it was found that the piezoelectric activity of the intermediate phase is the highest. © 2013 AIP Publishing LLC.