The chapter discusses the advancement in hydrogenation techniques for preparing black TiO2 and its significance in photoelectrochemical (PEC) hydrogen production. Black TiO2 has gained attention due to its high light absorption and photocatalytic capabilities. Traditional metal oxide semiconductors like Fe2O3 and BiVO4 face limitations in solar energy conversion efficiency. TiO2, though a promising photocatalyst, struggles with absorbing visible light. The chapter introduces two innovative hydrogenation methods, low temperature hot wire H and room temperature H+, to enhance TiO2 nanorods' photocurrent density for improved solar-to-hydrogen conversion efficiency. These methods aim to address issues like high temperature, pressure, and lengthy treatment associated with conventional hydrogenation techniques. The research focuses on developing cost-effective, efficient technologies for large-scale practical applications beyond state-of-the-art methods. Overall, the sentiment towards hydrogen in the chapter is positive, highlighting the advancements in black TiO2 hydrogenation and its potential for sustainable energy solutions.