Doping effects of Pt and Ru on Ni/Mg(Al)O catalysts were compared in daily start-up and shut-down operations of steam reforming of CH4. Trace Pt-doped catalyst showed better behavior than trace Ru-doped catalyst; the former was self-activated but the latter was not although both exhibited self-regenerative activity. Moreover, the former exhibited sustainable activity, although the latter was quickly passivated, in the autothermal reforming of CH4. Formation of Pt-Ni alloy on the surface of fine Ni metal particles on the catalysts was suggested by EXAFS analyses. CH4 was dissociatively activated to form hydrogen on Pt, assisted by adsorbed O or CH species, leading to the self-activation via Ni reduction by hydrogen spillover from Pt. The self-regeneration of the Pt-Ni/Mg(Al)O catalysts can be achieved by the continuous rebirth of active Ni metal species via reversible reduction-oxidation between Ni-0 and Ni2+ in/on Mg(Ni,Al)O periclase assisted by the hydrogen spillover. (C) 2008 Published by Elsevier B.V.