Varying the composition of Sr-Al oxides, mixed as well as single phase compounds were prepared and characterized extensively by XRD, NMR, TEM, EPR, XPS, and TPD. Depending on synthesis method and precursors, Sr/Al-based materials with different crystalline phases (e.g., Sr3Al4O9 center dot 2H(2)O, double perovskite, SrAl4O7. SrAl2O4, and SrCO3) were obtained. Apart from these crystalline phases, several other species were present, as identified by solid state NMR and TG-MS. The ratio of tetrahedrally to octahedrally coordinated Al (Al-IV/Al-VI) in the Sr/Al mixed oxides increased from 0.5 (pure alumina) to 5.2 in Sr/Al = 1.25, as determined by solid state NMR. The performance of these catalysts in the oxidative coupling of methane depended on the Al-IV/Al-VI ratio, both activity as well as C2+, selectivity increased with increasing Sr-content. The catalyst with a Sr/AI ratio of 1.25 showed a performance comparable to the well-known catalyst 1.9%Mn-4%Na2WO4/SiO2 under the conditions used (810 degrees C, CH4:O-2 = 108:22, GHSV similar to 26,000 L/kg(cat) h). (C) 2011 Elsevier Inc. All rights reserved.