For the first time, the fabrication of novel nanorods by the addition of polyaniline (PANI) to polyethylene oxide (PEO) and polyvinyl alcohol (PVA) polymers through electrospinning method is investigated. Field emission scanning electron microscopy observations reveal the formation of nanofibers and nanorods having diameters in the range of 26.87-139.90 nm and 64.11-122.40 nm, respectively, and lengths in the range of 542.10 nm to 1.32 μm. Photoluminescence (PL) analysis shows the presence of peaks which are characteristic of isotactic polymers (363-412, 529-691 nm), 412-529 nm for PVA/PEO and 363-691 nm for PVA/PEO/PANI. PL spectra also show peak bonding at a wavelength of 552 nm. Manufacture of nanorods by electrospinning method gives better options for controlling the diameter and length of nanorods.