A near MPB composition of 0.64PMN–0.36PT ceramic has been synthesized by solid-state reaction technique using columbite precursor. Sintering at 1030 °C resulted in a single perovskite phase with tetragonal structure having uniform and dense microstructure as revealed by powder XRD, Raman spectroscopy and FESEM analyses. An excellent dielectric response was obtained with room temperature dielectric permittivity value of 142 and high-phase transition temperature (Tm) of 210 °C at 1 kHz. A huge value of piezoelectric charge coefficient (490 pC/N) was obtained, which shows potential of PMN–PT for piezoelectric device applications. Well-shaped and fatigue-free P–E hysteresis loops over a wide temperature range of 30–230 °C were traced. A very large value of pyroelectric coefficient (p ∼ 2739.2 μC m−2 °C−1) was obtained.