Alumina supported vanadia catalysts were prepared by the wet impregnation method. The effect of vanadium content was investigated with 1.92-16.93 wt% V2O5 loading over the support. Physical characterization of the catalysts was done by techniques such as energy dispersive X-ray (EDX), X-ray diffraction (XRD), BET surface area measurement, FTIR spectroscopy and temperature programmed reduction (TPR) studies. Characterization techniques have revealed that vanadia is well dispersed over alumina up to 13.91 wt%, after which aggregation into vanadia crystallites was observed. Single step liquid-phase hydroxylation of benzene to phenol by hydrogen peroxide was studied over these catalysts. The phenol selectivity can be attributed to amorphous surface vanadyl units in the catalysts. The supported analogues were modified with oxides of iron and cerium. Ceria incorporation to alumina enhanced the activity towards hydroxylation of benzene.