Gasification converts biomass into syngas; however, severe cleaning processes are necessary due to the presence of tars, particulates and contaminants. The aim of this work is to propose a cleaning method system based on tar physical adsorption coupled with the production of pure H2 via a chemical looping process. Three fixed-bed reactors with a double-layer bed (NiO/Al2O3 and Fe-based particles) working in three different steps were used. First, NiO/Al2O3 is used to adsorb tar from syngas (300 °C); then, the adsorbed tar undergoes partial oxidization by NiO/Al2O3 to produce CO and H2 used for iron oxide reduction. In the third step, the reduced iron is oxidized with steam to produce pure H2 and to restore iron oxides. A double-layer fixed-bed reactor was fed alternatively by guaiacol and as tar model compounds, air and water were used. High-thermal-stability particles 60 wt% Fe2O3/40 wt% MgO synthetized by the coprecipitation method were used as Fe-based particles in six cycle tests. The adsorption efficiency of the NiO/Al2O3 bed is 98% and the gas phase formed is able to partially reduce iron, favoring the reduction kinetics. The efficiency of the process related to the H2 production after the first cycle is 35% and the amount of CO is less than 10 ppm.