Actualization of a hydrogen, rather than fossil fuel, economy requires H 2 storage, utilization and generation processes; the latter is the least developed of these technologies. Solar-energy driven water splitting combines several attractive features for energy utilization. The energy source (sun) and reactive media (water) for solar water splitting are readily available and are renewable, and the resultant fuel (generated H 2 ) and its discharge product (water) are each environmentally benign. This chapter presents an efficient renewable energy approach to produce H 2 fuel, the hybrid thermochemical solar generation of hydrogen. This energy source is capable of sustaining the highest solar-energy conversion efficiencies and fits well into a clean hydrogen energy cycle.To better understand the significance of an efficient solar hybrid hydrogen-formation process, it is useful to introduce it in the context of other solar hydrogen processes. Solar water splitting can provide clean, renewable sources of hydrogen fuel without greenhouse-gas evolution. A variety of approaches have been studied to achieve this important goal, for example, photosynthetic, direct or indirect photothermochemical, and photovoltaic or photoelectrochemical water splitting. As summarized in Table 21.1, each of these processes has exhibited a limited conversion of solar energy to hydrogen; photosynthetic, biological and photochemical solar water splitting [1][2][3][4][5] have exhibited solar energy to hydrogen conversion efficiencies, Z solar , on the order of only 1%; single [6-9] or multistep [10-14] photothermal