A new family of rhenium-based catalysts bearing HZSM-5 zeolite exhibits remarkable performances for the catalytic dehydrocondensation of methane with CO/CO2 towards ethylene, benzene, and naphthalene in high selectivity of above 90% at 1-3 atm and 973-1023 K. In contrast to Mo/HZSM-5 catalysts, the EXAFS and TG/DTA/Mass studies reveal that the metallic Re on HZSM-5 zeolite is a catalytically active and stable phase for the reaction.