We developed a facile precursor-treatment approach for effective surface passivation of rutile TiO 2 nanowire photoanode to improve its performance in photoelectrochemical (PEC) water oxidation. The approach was demonstrated by treating rutile TiO 2 nanowires with titanium precursor solutions (TiCl 4 , Ti(OBu) 4 , or Ti(OiP) 4 ) followed by a post annealing process, which resulted in the additional deposition of anatase TiO 2 layer on the nanowire surface. Compared to pristine TiO 2 , all the precursor-treated TiO 2 nanowire electrodes exhibited a significantly enhanced photocurrent density under white light illumination. Among the three precursor-treated samples, Ti(OBu) 4 -treated TiO 2 nanowires achieved the largest enhancement of photocurrent generation, which is approximately a 3-fold increase over pristine TiO 2 . Monochromatic incident photon-to-electron conversion efficiency (IPCE) measurements showed that the improvement of PEC performance was dominated by the enhanced photoactivity of TiO 2 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 TiO 2 nanowire electrodes for PEC water oxidation. This approach could also potentially be used for other photoconversion applications, such as TiO 2 based dyesensitized solar cells, as well as photocatalytic systems. electrodes were 0.039, 0.081, 0.043 and 0.045 mole/cm 2 , respectively. This result signified that the apparent surface area of the TiO 2 -TIP and TiO 2 -TBU electrodes were equivalent to that of the pristine TiO 2 electrode, while the TiO 2 -TCL electrode with rough surface had approximately twice the surface area of the pristine TiO 2 . This phenomenon further supported that the improved PEC performance of the TiO 2 -TIP and TiO 2 -TBU electrodes was related to effective surface passivation rather than an increase in surface area. As for the TiO 2 -TCL electrode, the improved PEC performance could be partly ascribed to the surface area effect because the increase in surface area was evident. Figure 5. (a) Absorption spectra for pristine TiO 2 and precursor-treated TiO 2 nanowire array films. (b) Absorption spectra for the N3-adsorbed samples after they were immersed into a base solution for N3 desorption. Inset shows the corresponding apparent color of the samples.