A multi-step process that employs a Ni-modified mixed alkaline earth metal oxides (AEMO) has been developed for the selective conversion of hydrocarbons to C2H2 and CO. The initial process step is the catalytic decomposition of a gaseous hydrocarbon mixture at an elevated temperature (ca. 800 degrees C) over Ni/AEMO, generating H-2, trace CO, carbon (C), and trace alkaline earth metal carbide (MC2). The Ni/AEMO/C/MC2 material is then heated to consume the remaining carbon, generate more MC2, and evolve CO. Then, Ni/AEMO/MC2 is cooled and reacted with excess H2O at a low temperature (20 < T (degrees C) < 80) to selectively generate C2H2 and Ni/AEM(OH)(2)center dot zH(2)O- In the final process step, Ni/AENl(OH)2 center dot zH(2)O is decomposed to yield H2O and Ni/AEMO, which is recycled within the process. The most advanced Ni/AEMO materials developed thus far exhibit intrinsic production capacities exceeding 2000 mu moles Of C2H2 per gram of Ni/AEMO per process cycle. (c) 2007 Elsevier B.V. All rights reserved.