The influences of annealing temperature on the phase transition, dielectrical, and ferroelectric response of 0.65Pb(Mg1/3Nb2/3)O-3-0.35PbTiO(3) (PMN-35PT) have been investigated in detail. X-ray diffraction combined with Raman spectra analysis indicated that the samples annealed below 1100 degrees C show a complete perovskite structure while at higher temperature, the volatilization of PbO results in the formation of the pyrochlore phase. The relative intensity I-740/I-800 of A(1g) mode increased with the increase of annealing temperature, indicating the phase transition to the tetragonal side. The annealing can eliminate the grain-boundary layer, release the internal stress, and improve the homogeneous distribution of polar nanoregions, resulting in the increase of dielectric constants and the decrease of relaxor behavior. Moreover, the squareness R-sq from the P-E hysteresis loop displayed the enhanced trend with the increase of annealing temperature, which can be attributed to the descending of B-site cation order.