Vanadia supported on praseodymia (2, 6 and 10 wt.% V2O5) were prepared by wet impregnation and characterized by energy dispersive X-ray analysis (EDAX), X-ray diffraction (XRD), TGA/DTA and BET surface area measurements. Decomposition of cyclohexanol was conducted over these catalysts in the vapor phase. Acidity of the catalysts was measured by temperature programmed desorption using ammonia as a probe molecule. The structural and acidic properties were correlated to the total conversion and cyclohexene selectivity.