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A nonanuclear CuII4TiIV5 heterometallic cluster, [Ti5Cu4O6(ba)16] (1, Hba=benzoic acid) was synthesized in one-pot reaction under the solvothermal condition. The metallic skeleton 1 contains a Ti5 core constructed from two vertex-shared Ti3 triangles and four separated Cu atoms outside which are connectedtogetherby μ3-O2- ions. Total16 ba- ligands adopt μ2-η1: η1 coordinationmode to protect the overall heterometallic core. Due to the unique d-d transitions of CuII ion, the reflectance spectrum of 1 displays broad and strong absorption towards visible light extending to the near-infrared region. Moreover, 1 shows almost purely paramagnetic behavior with the presence of weak antiferromagnetic interactions at low temperatures.