The addition of CO2 to the dehydrogenation of ethylbenzene (EB) to styrene over promoted and unpromoted vanadia, iron, and chromia catalysts on alumina improves the yield of styrene, in comparison with the use of N-2 as diluent. Depending on the catalyst, EB conversion increases 5-10%, while selectivity does not change significantly. The potassium promoted vanadium catalyst shows the highest CO2 conversion for dehydrogenation with the largest increase in EB conversion. The activity of these catalysts in the reverse water-gas-shift (RWGS) reaction, in the presence and absence of the dehydrogenation, is very different. Vanadium catalysts exhibit the lowest CO2 RWGS activity. The presence of coke on the catalyst suppresses the RWGS reaction over chromium and iron catalysts, but improves the activity of the vanadium catalyst. This is attributed to hydrogen spill-over from the coke to the metal catalyst. A two-step mechanism with a hydrogen spill-over is proposed for the EB dehydrogenation in CO2. Step-response experiments show that the redox mechanism for the RWGS and the two-step pathway for dehydrogenadon in CO2 are the dominant routes. A slight RWGS activity of the bare alumina support is attributed to an associative mechanism. (C) 2012 Elsevier B.V. All rights reserved.