Three-dimensional mesoporous TiO₂ scaffolds of anatase phase possess inherent eximious optical behavior that is beneficial for photoelectrodes used for solar energy conversion applications. In this regard; substantial efforts have been devoted to maximizing the UV and/or visible light absorption efficiency; and suppressing the annihilation of photogenerated charged species; in pristine mesoporous TiO₂ structures for improved solar illumination conversion efficiency. This study provides fundamental insights into the use of Mxene functionalized mesoporous TiO₂ as a photoelectrode. This novel combination of Mxene functionalized TiO₂ electrodes with and without TiCl₄ treatment was successfully optimized to intensify the process of photon absorption; charge segregation and photocurrent; resulting in superior photoelectrode performance. The photocurrent measurements of the prepared photoelectrodes were significantly enhanced with increased contents of Mxene due to improved absorption efficiency within the visible region; as verified by UV–Vis absorption spectroscopy. The anatase phase of TiO₂ was significantly augmented due to increased contents of Mxene and postdeposition heat treatments; as evidenced by structural analysis. Consequently; an appreciable coverage of well-developed grains on the FTO surface was observed in SEM images. As such; these newly fabricated conductive mesoporous TiO₂ photoelectrodes are potential candidates for photoinduced energy conversion and storage applications.