Wide bandgap semiconductors such as Zinc Oxide (ZnO) have earned much attention on account of its interesting optical and electrical properties. Also, doping ZnO with suitable transition elements enables to tune its properties, making it suitable for applications like transparent conducting oxides and LEDs. To this aim, Vanadium-doped ZnO (V:ZnO) thin films are fabricated using the SILAR method and studied the structural, optical, vibrational, photophysical and electrical properties. Introducing vanadium creates lattice relaxation in the ZnO wurtzite structure, influencing its electronic band structure. The X-ray diffraction (XRD) analyses have verified the structural integrity of the vanadium-doped zinc oxide (V:ZnO) films, revealing their polycrystalline composition. The Raman spectroscopy shows the reduced phonon line widths due to the improved crystallite quality with the presence of vanadium. Furthermore, it has been noted that optical characteristics such as the bandgap and refractive index are sensitive to vanadium doping as a consequence of modified electronic structures. Hall-effect experiments have shown that undoped ZnO films possess a mobility of 1.31 cm2/Vs and a charge carrier density of 5.58 × 1013 cm−3. It has been observed that doping with V markedly influences these parameters of ZnO films. Then, the time-resolved photoluminescence measurements reveal the increased carrier lifetimes, suggesting the introduction of dopants mitigates carrier-phonon interactions. Such interactions need to be minimized to prevent the dissipation of carrier energy. In essence, the reported work demonstrates the potential of V:ZnO for optoelectronic applications.