Metal-oxide-based electrodes play a crucial role in various transparent conductive oxide (TCO) applications. Among the p-type materials, nickel oxide is a promising electrically conductive material due to its good stability, large bandgap, and deep valence band. Here, we display pristine and 3 at.%V-doped NiO synthesized by the solvothermal decomposition method. The properties of both the pristine and 3 at.%V:NiO nanoparticles were characterized by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray diffractometry (XRD), Raman spectroscopy, ultraviolet–visible spectroscopy (UV–vis), and X-ray photoelectron spectroscopy (XPS). The film properties were characterized by atomic force microscopy (AFM) and a source meter. Our results suggest that incorporation of vanadium into the NiO lattice significantly improves both electrical conductivity and hole extraction. Also, 3 at.%V:NiO exhibits a lower crystalline size when compared to pristine nickel oxide, which maintains the reduction of surface roughness. These results indicate that vanadium is an excellent dopant for NiO.