The paper presents the results on the rapid production of H2 from CH4 by its direct decomposition in a plasma-catalytic mode stimulated by microwave irradiation (MWI) at 600°C. Methane was passed through a bed of iron-containing carbon adsorbent obtained from gas coal characterized by a large dielectric loss tangent. Under MWI, intense breakdown effects with plasma generation appear on the surface of the iron–carbon system. Methane in the plasma converts to hydrogen and carbon. A method has been developed for the rapid regeneration of the catalyst by water vapor with the removal of carbon under microwave stimulation. Short-cycle experiments have shown that the catalytic system provides high conversions of methane and its almost complete regeneration.