This aim of the percent work is to develop new, cost effective, high performance, lightweight polymer matrix composite nanofiber for corrosion resistance of aluminum in 0.1 M hydrochloric acid (0.1 M HCl) solution. Cerium oxide nanoparticles (ceria NPs) are embedded in-situ in poly vinyl chloride (PVC) solution, and then formed as nanofibers using electrospinning technique. The formed nanocomposite coating of PVC is successfully deposited on aluminum substrates; considering these substrates as metallic target in the electrospinning procedure. Measurements of corrosion for aluminum substrate before, and after coating with polymer nanofiber in 0.1 M HCl solution is performed using potentiodynamic polarization, and electrochemical impedance spectroscopy techniques. Potentiodynamic polarization and electrochemical impedance results confirm that ceria NPS embedded in-situ within PVC NFS coatings protect the aluminum surface from being corroded through minimizing both of its corrosion rate, corrosion current and increasing the surfaces' polarization resistance. The morphologies of polymer nanofiber coatings are imaged using scanning electron microscopy (SEM), with detecting the optical characteristics of the synthesized nanocomposite to prove the existence of oxygen vacancies associated to tri-valent cerium ions via optical analysis such as direct band gap, and fluorescence measurements. These vacancies are considered physical adsorbers for radicals which consequently reduces the corrosion rate. Average mean diameter of ceria NPS was measured using transmission electron microscopy (TEM).