Rare earth (RE = La3+, Sm3+, Pr3+) ion doped Pb(Mg1/3Nb2/3)O3–PbTiO3 (RE–PMN–PT) ferroelectric thin films with compositions near the morphotropic phase boundary were grown on the Pt/TiO2/SiO2/Si(100) substrate using sol–gel/spin coating method. The phase structure, electrical properties, and photoluminescence performance of thin films were investigated systematically. The highly (100)-preferred orientation was obtained in pure perovskite Sm–PMN–0.30PT thin films with an average grain size of 131 nm. After 2.5％ Sm3+ doping, the PMN–0.30PT thin films exhibited a triple enhancement of dielectric permittivity with a maximum value of 3500 at 1 kHz, a low dielectric loss of 1.3％, and high remanent polarization of 17.5 μC/cm2 at room temperature. In visible light and near-infrared band, the transmittance rate increased with PT content and showed the highest value of 85％ in 2.5％Sm–PMN–0.31PT. In addition, the films presented strong red-orange emission at 599 nm, which was sensitively in temperature range of 248–273 K corresponding to the rhombohedral to monoclinic phase transition temperature.