For these recent several years, biomass, geothermal, wind power, and the solar power becomes the urgent issues from a development demand that arise from global environment such as the running out crisis of the fossil fuel. However, there are not so many electric power generation systems in conjunction with the ocean accounting for 70% of the surface area of the earth. In the present work, we tried it using marine environment and solar for the purpose of improving a performance of the biofilm battery which was one of the microbial fuel cells (MFC). The biofilm formed to a cathode electrode ennoble the electrode potential and the photocatalytic effect of the TiO2 film coated metal surface of an anode electrode makes it possible to be an renewable energy source.However, we are not yet put it to a practical use by a reason such the lack of stability in the photocatalytic effect of the titanium dioxide coated on to the stainless steel anode by a plasma spraying technique. Therefore, in this study, we aimed to improve the photocatalytic activity of the anode electrode by developing the electrode which layered titanium dioxide by two phases using the the squeegee method and a plasma gas arc spraying method by improving those properties in the biofilm battery. As a result of measured electrode potential of the TiO2 electrode, following results were obtained;1) The photocatalytic potential of the TiO2 single-layered electrode showed -0.63V (SCE). This made the electrode potential lower 0.13V than that of an electrode conventionally, and improvement of the photocatalytic activity. In addition, reproducibility and stability were observed in the time variations of photo potential. When this electrode assembled in a biofilm battery, the open circuit voltage rose 0.09V in comparison with a battery conventionally, and the maximum power increase 1.33 times enabled.2) The output of the biofilm battery which assembling double layer TiO2 anode electrode rose 1.81 times electric power in comparison with previous one. It is thought that the electron which moves from the anatase outer layer to substrate stainless steel through the rutile intermediate layer accelerated by the heterojunction effect at the anatase / rutile interface.