CH4 decomposition over a wood char was investigated as an alternative green catalyst to produce hydrogen from hydrocarbons. Pyrolytic carbon (pyrocarbon) deposition leads to apparent deactivation of the catalyst by pore-mouth plugging. The activity of the carbon bed and its available surface area are easily restored by H2O gasification. The used char with pyrocarbon deposition was even found to be more reactive to gasification than the fresh char used in our conditions. This finding was highlighted by: (i) determination of gasification reaction extents by steam, (ii) temperature-programmed oxidation (TPO) of the fresh, used and reactivated chars and (iii) TPO under differential scanning calorimetry of these chars and demineralised chars. High-resolution transmission electron microscope (HRTEM) analysis of the chars showed different multiscale organisation of the carbon materials (disordered and graphitic mesoporous nanostructures). The fast regeneration of the used char could be attributed to the catalytic effect of the minerals present in the char that are reduced under our conditions of CH4 conversion. The predominant oxidation of the pyrocarbon compared to the char during its regeneration is evidenced through differential annealing (at 1800 °C) followed by XRD analysis. The oxidation of pyrocarbon is faster than the oxidation of the weakly reactive mesoporous carbon in char as shown by the HRTEM analysis. Consequently, wood char is an effective, easy to regenerate and cheap catalyst for converting hydrocarbons (CH4 or tar) into syngas.