A potential photocatalyst with 2 atom % vanadium incorporated into the 1 lattice of disordered mesoporous titania, Ti0.98V0.02O2, (TV2) was synthesized. Au was deposited on TV2 (Au/TV2) through a photodeposition method. Structural, microscopy, and spectroscopy techniques support the incorporation of vanadium into the TiO2 lattice, and Au was deposited on the surfaces of TV2. Photocatalytic oxidation of benzene was conducted at ambient temperature under UV and/or visible light to demonstrate the catalytic activity of the Au/TV2 catalyst. The TV2 lattice exhibits a quantum jump in benzene to phenol oxidation compared to that of TiO2, highlighting the importance of V for oxidation. Introduction of Au onto TV2 further increases the benzene to phenol oxidation and phenol yield by a factor of 2 under UV light compared to those of bare TV2. No significant phenol production was observed in visible light with or without gold, indicating the role of gold is indirect toward charge separation and electron storage. Nano gold clusters on TV2 selectively store photoexcited electrons and in turn maximize holes utilization on TiO2. The high photocatalytic activity of Au/TV2 is mainly attributed to the presence of Schottky junctions, disordered mesoporosity, and short diffusion lengths for charge carriers.