Six crystalline polyoxo-titanium clusters (PTCs) derived from oximes, namely, Ti(μ-O)(OMe)(L1) (PTC-125; HL1 = salicylaldoxime), H[Ti(μ-O)(μ-O)(OMe)(L1)] (PTC-126), Ti(μ-O)(μ-O)(O Pr)(OAc)(L2) (PTC-127; HL2 = salicylhydroxamic acid; HOAc = acetic acid), Ti(μ-O)(OEt)(L2) (PTC-128), Ti(μ-O)(μ-O)(OEt)(L2) (PTC-129), and Ti(μ-O)(μ-O)(μ-O)(OEt)(L3) (PTC-130; HL3 = acetoxime) have been solvothermally synthesized and structurally characterized. Compared with the reported solid-state monomer, dimer, trimer, and tetramer titanium oximes, these compounds possess high nuclearity structures in the range Ti, Ti, Ti, Ti, Ti, and Ti as a result of the presence of oxo bridges. Even though three examples of tetranuclear and hexanuclear derivatives have been documented, PTC-130 with a centrosymmetric Ti cluster core represents the currently highest PTC compound in the oxime system. In addition, Ti/oximate ratio by solvothermal synthesis in this work possessed a broad range from 0.83:1 to 9:1, different from the constant ratio of 1:1 in the reported ones. According to the solid-state UV-vis diffuse reflectance measurement, the existence of oxime ligands largely enhanced their visible light harvest. Furthermore, their photocurrent response properties are also studied.