Local lattice structures of 0.24Pb(InNb)O–0.43Pb(MgNb)O–0.33PbTiO (0.24PIN–0.43PMN–0.33PT) single crystal have been investigated by Micro-Raman spectroscopy. A total of 12 Raman active modes were ascertained using the Gauss–Lorentzian line shape approximation, which confirmed that the 0.43PIN–0.26PMN–0.33PT single crystal has monoclinic symmetry at room temperature. The phase transitions were investigated by analyzing the temperature-dependent relative dielectric permittivity of both poled and unpoled 0.43PIN–0.26PMN–0.33PT single crystals measured upon heating. The monoclinic–tetragonal phase transition occurs at T = 82 °C, and the Curie temperature is 199 °C. The splitting of (200) and (002) peaks in detailed X-ray diffraction spectra in the 2θ range of 44.6–45.2° during heating from room temperature to 200 °C was also studied. For a sample being poled along  pseudo-cubic direction, several sharp peaks arise in the thermally stimulated depolarization current from 67 to 82 °C with the main peak occurs at 67 °C, which indicates that the depolarization temperature is 15 °C lower than the monoclinic to tetragonal phase transition and there are coexistence of monoclinic and rhombohedral phases in the poled single crystal.
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