We developed a facile precursor-treatment approach for effective surface passivation of rutile TiO2 nanowire photoanode to improve its performance in photoelectrochemical (PEC) water oxidation. The approach was demonstrated by treating rutile TiO2 nanowires with titanium precursor solutions (TiCl4, Ti(OBu)4, or Ti(OiP) 4) followed by a postannealing process, which resulted in the additional deposition of anatase TiO2 layer on the nanowire surface. Compared to pristine TiO2, all the precursor-treated TiO2 nanowire electrodes exhibited a significantly enhanced photocurrent density under white light illumination. Among the three precursor-treated samples, Ti(OBu)4-treated TiO2 nanowires achieved the largest enhancement of photocurrent generation, which is approximately a 3-fold increase over pristine TiO2. Monochromatic incident photon-to-electron conversion efficiency (IPCE) measurements showed that the improvement of PEC performance was dominated by the enhanced photoactivity of TiO2 in the UV region. The photovoltage and electrochemical impedance spectroscopy (EIS) measurements showed that the enhanced photoactivity can be attributed to the improved charge transfer as a result of effective surface state passivation. This work demonstrates a facile, low-cost, and efficient method for preparing highly photoactive TiO2 nanowire electrodes for PEC water oxidation. This approach could also potentially be used for other photoconversion applications, such as TiO2 based dye-sensitized solar cells, as well as photocatalytic systems.