The electronic properties of the interfacial oxide film formed on 304L stainless steel in high temperature water are investigated by contact electric resistance (CER) measurements. Tests are performed in pure water with a wide range of dissolved oxygen (DO) content at 200, 250, and 288°C. The electrochemical potential (ECP) moves in the noble direction and CER increases when increasing DO. Results show that DO content has a dominant effect on the electronic properties of oxide film. The change of oxide film properties can also be attributed to the variation of the electrochemical potential, which is directly affected by DO content. Critical potentials exist for the formation and reduction of oxide films in high temperature water. Multiple steps are found for the reduction of oxide films due to de-aeration in 200, 250, and 288°C water, implying the presence of multiple-layer interfacial oxide films. The film reduction process is relatively slower than the film formation process. Present results show that even in high purity water, a moderate change of DO content can result in different surface conditions. Dissolved hydrogen has a moderate effect on interfacial surface films in deaerated water. In-situ monitoring of the oxide film properties by CER technique provides information on the interfacial reactions that are related to the SCC behavior of materials in high temperature water environments.