Nickel oxide nanowires modified by poly(vinylpyrrolidone) (PVP) were synthesized via a simple chemical pattern. For the first time NiO nanowires with diameters ranging from 40 to 100 nm with the expected ratio (length vs diameter) ranging from 54 to 90 were grown using a simple solution-phase approach (mild method). These nickel nanowires exhibited unique photoluminescence features and displayed a significant UV luminescence. X-ray absorption near-edge spectroscopy has been used to characterize the local Ni environment and identify the electronic structure. Comparing experimental and theoretical spectra at the Ni and O K edges, we determine the lattice distortion via the analysis of the characteristic preedge features and the multiple-scattering structures detected in the X-ray absorption near-edge structure spectra. The correlation between experimental features and the disordered or distorted local structures is also discussed.