Vanadia/ceria catalysts (2–10wt% of V 2 O 5 ) were prepared by wet impregnation of ammonium metavanadate in oxalic acid solution. Structural characterization was done with energy dispersive X-ray analysis (EDX), powder X-ray diffraction (XRD), BET surface area measurements, FT-IR spectroscopy and nuclear magnetic spectral analysis ( 51 V MASNMR). XRD and 51 V MASNMR results show highly dispersed vanadia species at lower loadings and the formation of CeVO 4 phase at higher V 2 O 5 loading. The catalytic activity of catalysts was conducted in liquid phase oxidation of ethylbenzene with H 2 O 2 as oxidant. The oxidation activity is increased with loading up to 8wt% V 2 O 5 and then decreased with further increase in V 2 O 5 content to 10wt%. Different vanadia species evidenced by various techniques were found to be selective towards ethylbenzene oxidation. The CeVO 4 formation associated with increased concentration of vanadia on ceria results the production of acetophenone along with 2-hydroxyacetophenone.