Thermochromic VO2 nanoparticles have been dispersed into polyvinyl pyrrolidone (PVP) fibers by electrospinning of a VO2-PVP blend solution. The structure and optical properties of the obtained composite fiber mat were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet visible (UV-Vis) spectrophotometry, and Fourier transform infrared (FT-IR) spectroscopy. The fiber mat revealed two diffuse reflectance states in infrared spectral region at temperatures under and above the phase transition temperature of VO2 and its IR reflectance is smaller in high temperature. The difference of diffuse reflectance between the two states (Delta R-dif) was obvious to be more than 25% in the wavelengths from 1.5 mu m to 6 mu m. The diffuse reflectance of the fiber mat could be controlled by adjusting the diameter of the fiber or the content of VO2 in the fibers and this particular optical property was explained by a multiple scattering-absorbing process.