The conversion of phenyl acetate over AlPO4 (Al/P=1), gamma-Al2O3 and SiO2 catalysts generated phenol, by deacetylation, and o-hydroxyacetophenone, by Fries rearrangement, as the main reaction products. The activity for Fries rearrangement was in accordance with the acidity data measured versus cyclohexene skeletal isomerization. Thus, AlPO4 showed the highest activity. Moreover, o-hydroxy-acetophenone formation increased with the reaction temperature. Besides, in AlPO4 catalysts 4-methylcoumarin and 2-methylchromone were also found, although in low amounts.