Polarized Raman spectra measurements have been performed on orientated single crystals of Pb[(Zn1/3Nb2/3)0.955Ti0.045]O3 (PZN-4.5%PT) and Pb[(Zn1/3Nb2/3)0.91Ti0.09]O3 (PZN-9%PT) poled by an electric field along the pseudo-cubic direction in order to determine the nature of the induced ferroelectric phases. Under field-cooled (FC) conditions the ferrolectric phase transition sequence, tetragonal–orthorhombic–rhombohedral, was observed in PZN-4.5%PT. Comparison between the phase transitions induced in PZN-9%PT and PZN-4.5%PT crystals in FC shows that the low- temperature ferroelectric phase in PZN-9%PT cannot be orthorhombic and it can be attributed to the monoclinic phase. The characteristic temperatures found by Raman spectroscopy correspond to those obtained by dielectric measurements and by X-ray diffraction reported previously.