Direct investigation of the electronic structure of catalyst surfaces on the near-atomic scale in general has not been impossible in the past. However, with the advent of the scanning tunneling microscope (STM), the opportunity arises for incorporating the scanning tunneling spectroscopy (STS) for correlation in-situ surface electronic structure with topography on a sub-nanometer scale. In this paper, we report the STS results of thin film TiO2 and Pt-deposited TiO2 annealed at 450℃. It was found that the TiO2 semiconductor changes from n-type to p-type after Pt deposition.Fig. 1 shows the surface electronic property (Ⅰ-Ⅴ curve) of thin TiO2 film measured in air by STS. A steep descent of the anodic tunneling current at ca.- 1.0 Ⅴ and a rapid ascent of cathodic tunneling current at ca. +2.0V. The zero bias represents the Fermi level (Ef). Ef is situated at the Ecb side indicating that the thin TiO2 film possesses the same band gap as that of bulk TiO2 phase ( Egs =3.0 to 3.2 eV). For the sample of Pt-deposited TiO2 film, Pt/(Pt+Ti+O) atomic ratio≈0.2, which indicates that the surface of TiO2 film is partly covered by Pt particles, and there are two types of Ⅰ-Ⅴ curves to be detected. One of them (Fig.2a)is attributed to the electronic property of TiO2, which has same Egs as that shown in Fig. 1. However, the Ef is transferred to valence side (△≈1eV). This phenomenon hints that TiO2 is doped by an impurity which can introduce h+ into TiO2 lattice.Such a type of defects may be described by Ti1-xPtxO2(h )2x, here Pt+2 as a substitutional site of Ti+4. Fig.2b is the Ⅰ-Ⅴ curve of a Pt particle situated on a TiO2 particle contained Ti1-xPtxO2(h )2x.