The chemical synthesis of TiO2 thin films on mixed self-assembly monolayers (SAMs) is reported. The mixed SAMs with different ratios of -SH and -SO3H groups were obtained when oxidized in H2O2/HOAc solution for various limes. Atomic force microscopy (AFM) demonstrated various growing modes of thin films that may be induced by -SH or other oxide states of sulfur groups in the mixed self-assembly monolayers. X-ray photoelectron spectroscopy (XPS) results illustrated that different oxidation states of titanium exist in the TiO2 films on the mixed SAMs.