We have demonstrated the N719 dye-SrTiO₃–TiO₂ system for the application in dye-sensitized solar cells, which is thermodynamically more favorable for electron transport and charge separation efficiency. The heterojunction SrTiO₃–TiO₂ photoanode with an enlarged pore diameter was fabricated by anodization of a Ti foil substrate and sequential hydrothermal reaction. Their photoelectrochemical properties were investigated as dye-sensitized solar cells for the first time. The optimal conditions for enlarged pore diameter of anodized TiO₂ nanotube arrays (TNTAs) were suggested using a tetraethylene glycol based electrolyte, and SrTiO₃ for the heterojunction photoanode was hydrothermally reacted on TNTAs. The structure and pore size of the hetero-structured SrTiO₃–TiO₂ nanotubes arrays (ST-TNTAs) were studied comparatively for their photocatalytic activity in parallel with various SrTiO₃ morphologies. The enhanced photocatalytic property of ST-TNTAs compared with TNTAs could be attributed to the enhanced suppression of charge recombination by the heterojunction of ST-TNTAs due to easier crossing of the interface of ST-TNTAs by more the negative conduction band potential of SrTiO₃. This is also possible because of the optimized interfacial area and the distance between SrTiO₃ nanoparticles and TNTAs. With electrochemical impedance spectroscopy, we report promising applications of dye-sensitized solar cells with the hetero-structured photoanode of ST-TNTAs for the first time.