Lead molybdate (PbMoO₄) materials were successfully synthesized using a facile surfactant-assisted microwave process and characterized by XRD, Raman, PL, BET and DRS. We also investigated the photocatalytic activity of these materials for the decomposition of Rhodamine B under UV-light irradiation. The XRD and Raman results revealed the successful synthesis of 42–69 nm, well-crystallized PbMoO₄ crystals with a facile surfactant-assisted microwave process. The PbMoO₄ catalysts prepared using microwave process enhanced the photocatalytic activity compared to PbMoO₄ catalyst prepared by hydrothermal method. The PbMoO₄ catalyst prepared at 100 °C showed the highest photocatalytic activity. The PL peak was appeared at about 540 nm for all catalysts and the excitonic PL signal was proportional to the photocatalytic activity for the decomposition of Rhodamine B.