Domain pattern variations with temperature were studied by polarizing light microscopy for the morphotropic phase boundary composition 0.67Pb(Mg1/3Nb2/3)O3−0.33PbTiO3 (PMN-0.33PT) single crystal. At room temperature, the monoclinic MA phase is the dominant phase in the unpoled crystal, which coexists with a small fraction of the tetragonal (T) phase. The orientation of spontaneous polarization was calculated to be ∼4.8∘ away from the pseudocubic 〈111〉C in the {001}C plane family. Under an electric field of 6 kV/cm along [011]C, a single domain orthorhombic (O) phase was induced but partially switched back to MA a few hours after the removal of the E field. It was found that the temperature induced phase transition sequence of the [011]C poled PMN-0.33PT single crystal is strongly hysteretic. On heating, the phase transition sequence is as follows: coexistence of O phase and MA→rhombohedral→monoclinicMC→cubic(C). On cooling, the phase transition sequence is given by C→T→MA. The complete set of dielectric, piezoelectric, and elastic constants for the [011]C poled PMN-0.33PT single crystal was measured, which showed the strong feature of the single domain O phase with high shear (d15=2321pC/N,d24=1941pC/N) and low longitudinal piezoelectric coefficients (d33=165pC/N).