Semiconductors with bandgaps and edges corresponding to the solar energy spectrum are found to be suitable for the water splitting applications using photoelectrochemical reactions. However, many present-day materials used in these applications do not have high stability and/or high effectiveness over the complete sunlight spectral range. The recently proposed eutectic compounds, which combine two or more semiconducting materials, can overcome many present difficulties and extend the light absorbance spectrum improving the effectiveness of the water splitting cells. Herein, structural and electronic properties studies of the SrTiO3–TiO2 eutectic material, which is a representative example of this family, are presented. It is found that structural properties of this material, particularly the phase separation and formation of the sharp interface between two phases, can be significantly improved up on the thermal annealing, which is very important for their application in the water splitting reactors. The findings present the deep understanding of the interface structure and electronic properties of the SrTiO3–TiO2 eutectic, which can help to improve the functionality of these class of materials in different applications.