The phase transformation sequence in as-grown PZN-4.5%PT single crystal has been investigated by means of dielectric permittivity measurements and high-resolution synchrotron x-ray diffraction. The results show that the crystal undergoes the R-T(R)-M c -C transformation path during zero-field heating from 25°C to 160°C, where R, T, M C and C are the rhombohedral, tetragonal, M C -type monoclinic, and cubic phases, respectively. "T(R)" represents that dominant T domains coexist with smaller fraction of R domains. Our results indicate that both the R-T and R-M c transformations are first-order, while the T-M c -C transformation is second-order in nature.