In this study, nickel acetate tetrahydrate (NACTH)/poly(styrene-co-acrylonitrile) (SAN) sol was used for the fabrication of nanocrystalline NiO nanofibers. An indigenous setup was developed to use these nanofibers for the oxidation of carbon monoxide (CO) and unburnt hydrocarbons (HC) from diesel engine exhaust. The morphological, compositional, and crystalline properties of the NiO nanofibers obtained after calcination were studied by scanning electron microscopy, Fourier transform infrared (FTIR) spectroscopy, and x-ray diffraction (XRD). Clear evidence of defects in the fibers was observed in ultraviolet–visible–near infrared (UV-Vis-NIR) spectra, Raman spectra, and magnetic property measurements. The NiO nanofiber mats supported by glass fiber mats were efficient in oxidizing CO and HC from diesel engine exhaust, and the maximum efficiency was achieved by using NiO nanofibers with the maximum amount of defects.