Silica-supported tantalum hydride, ( SiO)(2)Ta-H (1), proves to be the first single-site catalyst for the direct non-oxidative coupling transformation of methane into ethane and hydrogen at moderate temperatures, with a high selectivity (>98%). The reaction likely involves the tantalum-methyl-methylidene species as a key intermediate, where the methyl ligand can migrate onto the tantalum-methylidene affording the tantalum-ethyl.