The phase-transition sequence of 0.67Pb(Mg1/3Nb2/3)-0.37PbTiO3 (PMN-0.37PT) single crystals driven by the electric (E) field and temperature is comprehensively studied. Based on the strain-E field loop, polarization-E field loop, and the evolution of domain configurations, the E field along the [011] C induced phase transitions have been confirmed to be as follows: tetragonal (T) → monoclinic (MC ) → single domain orthorhombic (O) phase. As the E field decreases, the induced O phase cannot be maintained and transformed to the MC phase, then to the coexistence state of MC and T phases. In addition, the complete sets of dielectric, piezoelectric, and elastic constants for the [011] C -poled domain-engineered PMN-0.37PT single crystal were measured at room temperature, which show high longitudinal dielectric, piezoelectric, and electromechanical properties ([Formula: see text], d33 = 1052 pC/N, and k33 = 0.766). Our results revealed that the MC phase plays an important role in the high electromechanical properties of this domain-engineered single crystal. The temperature dependence of the domain configuration revealed that the volume fraction of the MC phase decreases with temperature accompanied by the reduction of [Formula: see text], d31, and k31 due to the substantially smaller intrinsic properties of the T phase.