Nanofibers were synthesized by an electrospinning technique using a polymer as a support and polyoxometalates (POMs) as dopants. X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, P-31 MAS NMR, scanning electron microscopy (SEM), and a high resolution transmission electron microscope (TEM) were used to characterize the resulting hybrids. These POM nanofiber catalysts could provide a continuous flowing mode to promote the oxidative degradation of phenol into simpler inorganic species using air (O-2) as an oxidant at room temperature through nine cycles. The leaching of POMs from the nanofibers was minor, showing that the catalyst had excellent stability and could be used as a heterogeneous structure.