In situ high-resolution synchrotron x-ray diffraction, dielectric permittivity, hysteresis loop, and polarization current, were used to investigate phase transitions of (211)-cut 0.70Pb(Mg1/3Nb2/3)O3–0.30PbTiO3 single crystal before and after an electric (E) field poling. A rhombohedral (R)–tetragonal (T)–cubic transition sequence was observed upon zero-field heating in both unpoled and poled samples. Before the R–T transition takes place, an extra dielectric and polarization current anomalies near 365 K were observed in the poled sample due to a transition of polarization ordering. The direct piezoelectric coefficient d33 exhibits a rapid increase for poling at E=1.0–1.3 kV/cm, followed by an overpoling behavior. The increment of polarization ordering plays an important role while the high piezoelectric response builds up.