Gd-doped PbMoO4 nanoparticles were prepared by a refluxing method at 80 °C for 2 h. Effect of molar content of Gd dopant on phase, morphology and optical properties was studied. The as-prepared Gd-doped PbMoO4 samples can be indexed to pure tetragonal PbMoO4 phase. The particles size of PbMoO4 is decreased with increasing in the molar content of Gd dopant from 15.20 ± 3.04 nm for pure PbMoO4 to 8.72 ± 1.53 nm for 5 mol％Gd-doped PbMoO4. The absorption of 5 mol％Gd-doped PbMoO4 nanoparticles shows red-shift caused by lattice distortion of PbMoO4. The photocatalytic performance of 5 mol％ Gd-doped PbMoO4 nanoparticles shows the highest degradation of rhodamine B (RhB) of 97.92％ under UV radiation and 67.65％under visible radiation because Gd3+dopant as an electron acceptor plays the role in enhancing the separation of electron-hole pair.