Alumina supported vanadia catalysts (V/Al) for selective oxidehydrogenation of ethylbenzene with CO2 were prepared by impregnation method. During preparation the effect of promoters and calcined temperature was investigated, it was found these two items had a strong influence on the activity of V/Al catalysts. Dehydrogenation reaction with CO2 was happened in the fixed-bed reactor at 450 degrees C. Results showed that 15.2% ethylbenzene conversion and 99.2% styrene selectivity were acquired when V2K/Al catalyst was used.