PbO nanofibers were fabricated by calcination of the electrospun PVP/Pb (NO3)(2) composite nanofibers. For the first time, PbS nanofibers and PbSe nanofibers were successfully synthesized by double-crucible sulfurization and selenidation methods using PbO nanofibers as precursors, respectively. X-ray diffraction (XRD) analysis shows PbS nanofibers and PbSe nanofibers are respectively pure cubic phase with space group of Fm-3 m. Scanning electron microscope (SEM) observation indicates that the diameter of PbS nanofibers and PbSe nanofibers are 295.52 +/- A 25.43 and 265.31 +/- A 21.90 nm under the 95 % confidence level, respectively. The photocatalytic activities of samples were studied by using rhodamine B (Rh B) as degradation agent. When PbS or PbSe nanofibers are employed as the photocatalysts, the respective degradation rates of Rh B solution under the ultraviolet light irradiation after 220 min irradiation are 70.79 and 73.17 %. This preparation technique could be applied to prepare other metal chalcogenides nanofibers. The photocatalytic mechanism and formation process of PbS and PbSe nanofibers are also provided.