The objective of this study is to establish a potential technique for producing hydrogen-rich synthesis gas from waste wood at a lower temperature than conventional methods, as it has been proposed that the gas product be used as a fuel for a molten carbonate fuel cell (MCFC). To achieve this, experiments were conducted in a bench-scale experimental system, applying four kinds of commercial nickel (Ni)-based steam reforming catalysts. The experimental results indicated that hydrogen can be efficiently generated from biomass via high-temperature (950 °C) steam gasification. Conversely, the application of a catalyst was shown to have excellent effects on the hydrogen yield at lower temperatures. Of several catalysts used, the use of that containing a CaO component at 750 °C successfully generated hydrogen gas of about 55 vol%. The catalyst also helped reduce hydrogen sulfide that had prevented MCFC operation and toxic dioxins in the generated gas, and the performance was quantitatively evaluated.