Monoclinic VO2 nanorod thin films were deposited on indium‑tin-oxide-coated glass substrates using radio-frequency reactive magnetron sputtering at a substrate temperature of 300°C and various O2 flow rates. The thin films were characterized via standard analysis techniques. The VO2 thin films exhibited a highly crystalline monoclinic phase with an indirect band gap of ~1.73eV. At optimized O2 flow rate (4sccm), the thin films was observed nanorod structures, exhibited a remarkable photocurrent of ~0.08mAcm−2 during photoelectrochemical water splitting in the visible region. Electrochemical performance tests of the nanorod films revealed a specific capacitance of ~486mFcm−2 at a scan rate of 10mVs−1. In addition, amperometric I–t curves showed that VO2 thin film electrodes were highly stable during the photo-oxidation process. The nanorod films also exhibited a good specific capacitance of ~120mFcm−2 after 5000cycles at a scan rate of 100mVs−1. The photocurrents during photoelectrochemical water splitting and the specific capacitance of VO2 thin films deposited at O2 flow rates of 2 and 6sccm were 0.06 and 0.07mAcm−2 and 398 and 37mFcm−2, respectively. The films deposited under Ar at 8sccm and O2 at 4sccm showed the highest photoelectrochemical water splitting performance and specific capacitance, owing mainly to their nanorod-like morphology.