Serpentinization of peridotites involves the production of hydrogen, which is a source of vital energy for chemosynthetic communities and abiotic methane or other hydrocarbons. Serpentinite-hosted hydrothermal vent fields that discharge fluids with hydrogen have been widely noticed as a possible environment for the generation of life on the early Earth and other terrestrial planets. In this context, it is important for us to understand petrological constraints on serpentinization processes related to hydrogen production. Magnetite formation by oxidation of iron in olivine is the most effective process for hydrogen production during serpentinization. Recent petrological studies have revealed that the magnetite formation is controlled by silica activity and Fe-Mg diffusion rate in olivine crystal, as well as temperature and water/rock ratio during serpentinization. Without local elevation of silica activity via fluid infiltration, magnetite forms at temperatures ranging approximately from 150 to 350 °C with most favorable condition at around 300 °C, but fails to form because of increasing diffusion rate in olivine crystal at higher temperatures and Fe-serpentine or Fe-brucite formation at lower temperatures. It should be kept in mind, however, that the formation of oxidized serpentine could produce hydrogen as well.