A Ti₆-core-based titanium oxo cluster (TOC) [Ti₆(m₂-O)₂(m₃-O)₂(Bpo)₂(PhCOO)₈(OiPr)₄] assembled by 2,2΄-biphenol (H₂Bpo) and benzoic acid has been synthesized and characterized by IR, elemental analyses, thermogravimetric analysis and X-ray diffraction technique. Single-crystal X-ray diffraction analysis revealed that the complex crystallizes in monoclinic system, space group P2₁/n. The structure contains two Ti₃(m₃-O) units featuring a flat mode as building blocks. Solid-state UV/Vis absorption spectrum reveals that complex 1 shows a wide range from 240 to 650 nm. Moreover, the optical band gap of 1 is estimated to be 2.35 eV. Additionally, the Ti₆-TOC exhibits good photocurrent response.