The oxidative dehydrogenation of ethane into ethylene by carbon dioxide over unsupported Cr2O3, Cr2O3/SiO2 and a series of Cr2O3/SiO2 catalysts modified by sulfate was investigated. The results show that Cr2O3/SiO2 is an effective catalyst for dehydrogenation of ethane and CO2 in the feed promotes the catalytic activity. Sulfation of silica will influence the catalytic behavior of Cr2O3/SiO2 in dehydrogenation of ethane with carbon dioxide depending on the amount of sulfate. Cr2O3/6 wt% SO42-–SiO2 catalysts exhibit an excellent performance for this reaction, giving an ethylene yield of 55% at 67% ethane conversion at 650°C. Characterizations indicate that addition of sulfate changes the bulk and surface properties of Cr2O3/SiO2, promoting the reduction of Cr6+ to Cr3+ and favoring the catalytic conversion.