Biomass, including biogas, municipal organic waste, and lignocellulosic biomass, is considered the renewable raw material of choice for the future; it represents an energy and carbon source for the modern industrial system, with an enormous potential for reducing the greenhouse emissions and mitigating the fossil fuel dependence. In turn, H2 is a clean fuel and an energy carrier and also an important commodity in many industrial processes. Its distributed production in small-medium scale sites, exploiting renewable raw materials, may represent a promising solution for a massive penetration of highly-efficient co-generation systems based on fuel-cells (e.g. for residential heat and power cogeneration) (see schemes below).Additionally, in the future scenario of replacement of traditional oil refineries by biorefineries, the conversion of oxygenates into synthesis gas (a H2/CO mixture) is an intermediate step to the production of fuels, and chemical commodities (like ammonia and methanol). The overall consumption of H2 in biorefinery processes will be extremely high, and thus, the conversion of biorefinery by-products into H2-rich streams is thus extremely attractive.