Titanium dioxide (TiO2), renowned for its stability and abundance, is a benchmark photoanode for solar water splitting; however, limited visible-light absorption, polaronic charge recombination, and sluggish oxygen evolution hinder its redox efficiency. In this regard, we integrate hydroxyl-functionalized 2D NiCo-layered double hydroxide onto 1D TiO2 nanorods, enhancing hole transport, stabilizing Co centers, and suppressing polaron-induced charge recombination. Surface analysis revealed a high electrochemically active surface area (966.6 cm2) for TNR/NiCo@OH. Interface engineering with 2D/1D contact and hydroxyl grafting boosted photocurrent density to 1.46 mA cm−2, ∼2.5-fold higher than bare TNRs. The intricately engineered TNR/NiCo@OH photoanode achieved a photoconversion efficiency of 0.68 % and remained highly stable in alkaline media for ∼24 h without significant structural degradation. These findings establish a solid foundation for the advancement of efficient TiO2-based solar-assisted energy conversion systems through the combined integration of 1D/2D heterojunctions and surface hydroxyl engineering.