The article discusses the pressing need for clean energy solutions and environmental remediation methods due to pollution and the energy crisis. Photocatalysis, particularly with TiO2 and NiAl-LDHs, is highlighted as a promising approach for sustainable energy production and pollutant degradation. The study focuses on the development of a unique NiAl-LDH@TiO2-Tiv-S core-shell photoelectrocatalyst for efficient wastewater treatment and oxygen evolution reaction. By introducing sulfur dopants into Ti vacancies, the catalyst shows enhanced performance in degrading Rhodamine B dye and producing oxygen. Various factors affecting dye degradation and OER activity were investigated, showcasing the catalyst's potential for practical applications. Defect engineering strategies involving Ti vacancies and sulfur doping prove crucial in improving catalytic performance for both environmental and energy solutions.