Hydrogen production by water-splitting thermochemical cycle based on manganese ferrite/sodium carbonate reactive system is reported. Two different preparation procedures for manganese ferrite/sodium carbonate mixture were adopted and compared in terms of materials capability to cyclical hydrogen production. According to the first procedure conventionally synthesized manganese ferrite, i. e. high temperature (1250 °C) heating in Ar of carbonate/oxide precursors, was mixed with sodium carbonate. The blend was tested inside a TPD reactor using a cyclical hydrogen production/material regeneration scheme. After few cycles the mixture resulted rapidly passivated and unable to further produce hydrogen. An innovative method that avoids the high temperature synthesis of manganese ferrite is presented. This procedure consists in a set of consecutive thermal treatments of a manganese carbonate/sodium carbonate/iron oxide mixture in different environments (inert, oxidative, reducing) at temperatures not exceeding 750 © C. Such material, whose observed chemical composition consists in manganese ferrite and sodium carbonate in stoichiometric amount, is able to evolve hydrogen during 25 consecutive water-splitting cycles, with a small decrease in cyclical production efficiency. Copyright© 2008 by ASME.