The current work focuses on the fabrication of pristine and metals (Co, Cu, Ni, Li, and Sn) doped β-PbO phase nanoparticles by cost-effective precipitation method. The properties of the produced nanoparticles were investigated using a variety of characterization techniques. The produced compound was a highly pure β-PbO phase, according to the XRD data. From the UV–vis DRS the obtained bandgap of pristine β-PbO, Co, Cu, Ni, Li, and Sn doped β-PbO was 2.68 eV, 1.88 eV, 2.01 eV, 2.65 eV, 2.64 eV, and 2.70 eV, respectively. The doped samples with the lowest photoluminescence (PL) intensities show the reduced photogenerated electron–hole pair recombination, which increased the photocatalytic activity of β-PbO nanoparticles. The study of the surface morphology by SEM reveals the irregular distribution of the particles. In both pristine and doped nanoparticles, EDX verifies the existence of the expected elements. In comparison to pristine β-PbO, all doped β-PbO nanoparticles have enhanced photocatalytic activity for the degradation of methylene blue (MB) dye under the irradiation of visible light. Among the doped nanoparticles, Cu and Co-doped β-PbO demonstrated particularly high performance. After 80 min of irradiation, Cu and Co-doped β-PbO showed 99.45% and 99.39% degradation rates of MB dye, compared to only 75.13% for pure β-PbO. Hence, the photocatalytic activity of pure β-PbO is boosted through metals doping due to bandgap narrowing, generation of impurity states, increased specific surface area, higher carrier concentration, reduced carriers recombination, the action of dopant ions, and microstructural changes.