In this paper, composite fibers of polyvinylpyrrolidone (PVP) and Y2O3:Eu3+ nanocrytals were prepared by electrospinning and characterized by electron microscope, Fourier transform infrared spectra (FT-IR) and X-ray diffraction (XRD). The composite fibers are in random orientation and with average diameter of approximately 300 nm and length up to several ten micrometers. The luminescent properties were investigated and compared with the pure Y2O3:Eu3+ nanocrystals. Due to certain weak interactions between nanocrystals and PVP matrix, charge transfer band in the excitation spectra show slightly red shift for the fibers relative to in the case of pure Y2O3:Eu3+ nanocrystals. The PVP polymer may modified the surface defect states of nanocrystals, yielding decreased intensity ratio of 5Do-(7)F2 to (5)D0-(7)F1 transition in the emission spectra. The fluorescence lifetimes of (5)D0 level for Eu3+ in the composite fibers and Y203:Eu3+ nanocrystals were respectively determined to be 1.40 and 1.74 ms. The decreased fluorescence lifetime in the composite fibers was attributed to increased radiative transition rate, as result of the influence of refractive index of the surrounding PVP media instead of air.