In this work, microemulsion method has been followed to synthesize vanadium-doped Zn1−xVxO (with x = 0.0, 0.02, 0.04, 0.06, 0.08, and 0.10) nanoparticles. The prepared samples are characterized by several techniques to investigate the structural, morphology, electronic, functional bonding, and optical properties. X-ray diffractometer (XRD) analysis confirms the wurtzite phase of the undoped and V-doped ZnO nanoparticles. Variation in the lattice parameters ensures the incorporation of vanadium in the lattice of ZnO. Scanning electron microscopy (SEM) shows that by increasing contents of V ions, the average particle size increases gradually. X-ray Absorption Near Edge Spectroscopy (XANES) at the V L3,2 edge, oxygen K-edge, and Zn L3,2 edge reveals the presence and effect of vanadium contents in the Zn host lattice. Furthermore, the existence of chemical bonding and functional groups are also asserted by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR). UV–Visible analysis shows that by increasing V+ contents, a reduction up to 2.92 eV in the energy band gap is observed, which is probably due to an increase in the free electron concentration and change in the lattice parameters.