Aligned and unaligned vanadium (IV) oxide meso-tetraphenyl porphine (VMP)/polyethylene oxide (PEO) hybrid nanofibers have been successfully synthesized by electrospinning technique. The nanofibers were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), atomic force microscopy (AFM), optical microscopy and scanning electron microscopy (SEM). The SEM and AFM analyses of the morphology showed that the nanofibers are cylindrical with diameters ranging from 400-700nm. The AFM analysis also confirmed that the aligned nanofibers deposited on a small metallic spring are smoother than the unaligned ones deposited on FTO. FTIR analysis showed that the polar environment provided by the phenyl groups of VMP molecules modified the chemical configuration of PEO molecules, and XRD studies indicated that the VMP molecules were homogeneously distributed within the PEO matrix.