Co-promoted Na2WO4/Mn/SiO2 catalysts were prepared and used in the reaction of C2H6 with CO2. XRD, XPS techniques were employed to study the structure of the fresh and post-reacted catalysts. It was found that the existence of Co was in favor of the reforming of C2H6 to synthesis gas. The Co species were reduced into metal Co, which might act as the active phase for CO production. Over Co-promoted Na2WO4/Mn/SiO2 catalysts in the reaction process, the oxidative dehydrogenation and reforming of ethane by CO2 might be tuned. Under the conditions of C2H6/CO2 = 1/5, F= 60 ml/min, 750 degrees C, the catalyst dosage of 0.3 g, products with molar ratio of C2H4/CO/H-2 = 1/1/1 could be obtained from C2H6 and CO2, and could be used directly into hydroformylation to propanal. (C) 2009 Elsevier B.V. All rights reserved.