If one considers the largest and geographically balanced free natural resource available on Earth, that is seawater, and that more sunlight energy is striking our blue planet in one hour than all of our annual energy consumption, the direct solar-to-hydrogen conversion by photo-oxidation of seawater is a very straightforward and attractive solution for the production of hydrogen, as it is clean, sustainable and renewable. It offers an alternative solution to fossil-fuel-based energy sources and explains the tremendous interest in renewable, sustainable energy sources and materials for energy conversion. However, the materials requirements for water splitting and thus the direct solar-to-hydrogen generation are drastic. The materials must be stable in water, which rules out many classes of materials. They must also be stable under illumination against photocorrosion and their bandgap must be small enough to absorb visible light, but large enough not to “dissolve” once illuminated. Finally, their band edges must be positioned below and above the redox potential of hydrogen and oxygen, respectively. Bandgap energy and band-edge positions, as well as the overall band structure of semiconductors are of crucial importance in photoelectrochemical and photocatalytic applications. The energy position of the band edges can be controlled by the electronegativity of the dopants and solution pH, as well as by new concepts such as quantum confinement effects and the fabrication of novel hetero-nanostructures. Fulfilling those requirements while keeping the cost of the materials low is a tremendously difficult challenge, which explains why solar hydrogen generation is still in its infancy. Novel approach and latest development combining low cost aqueous synthesis techniques, vertically oriented metal oxide nanorods and quantum confinement effects probed by x-ray spectroscopies from synchrotron radiation is presented leading to stable and cost-effective visible-light-active semiconductors for seawater splitting, the holy grail of photocatalysis.