Photocatalytic water splitting holds great promise as a sustainable and cost‐effectiveness alternative for the production of hydrogen. Nevertheless, the practical implementation of this strategy is hindered by suboptimal visible light utilization and sluggish charge carrier dynamics, leading to low yield. MXene is a promising cocatalyst due to its high conductivity, abundance of active sites, tunable terminal functional groups, and great specific surface area. Homo‐interface has perfect lattice matching and uniform composition, which are more conducive to photogenerated carriers’ separation and migration. In this study, a novel ternary heterogeneous photocatalyst, a‐TiO₂/H‐TiO₂/Ti₃C₂ MXene (MXTi), is presented using an electrostatic self‐assembly method. Compared to commercial P25, pristine anatase, and rutile TiO₂, as‐prepared MXTi exhibit exceptional photocatalytic hydrogen evolution performance, achieving a rate of 0.387 mmol h⁻¹. The significant improvement is attributable to the synergistic effect of homo‐interface engineering and Ti₃C₂ MXene, which leads to widened light absorption and efficient carrier transportation. The findings highlight the potential of interface engineering and MXene cocatalyst loading as a proactive approach to enhance the performance of photocatalytic water splitting, paving the way for more sustainable and efficient hydrogen production.