Through electrospinning technique, the lanthanide complex with good luminescent property, Eu(DBM)3 · H2O and Eu(DBM)4 · CPC, were incorporated into water soluble polymer PVP, and the polymer nanofibers with red characteristic fluorescent light from europium ion were obtained. The microstructure of the rare earth complexes and polymer nanofibers product was studied by scanning electron microscopy and transmission electron microscopy, and the result indicated that when the rare earth complexes were compounded into the polymer nanofibers, it＇s microstructure changed due to its good compatibility with PVP ethanol solution, and the polymer nanofibers with one dimension were of 50-100 nm relatively uniform line shape structure. In addition, the fluorescence excitation and emission spectra and fluorescence lifetime of the rare earth complexes and polymer nanofibers product were studied. Photoluminescence measurements indicate that the lanthanide complexes show superior emission lines, higher intensities and longer fluorescent lifetime in the polymer nanofibers than in the corresponding pure complex powders, which is due to the composite nanofibers providing a relatively stable environment for lanthanide complexes.