The vapour phase reaction of phenol with ethyl acetate was investigated over Al-MCM-41 with Si/Al = 55 and 80, and (Al, Zn)-MCM-41 with Si/(Al + Zn) = 52 at 200, 250, 300, 350 and 400degreesC. The products were phenyl acetate (PA), 2-ethylphenol (2-EP), 2-acetylphenol (2-AP) and 4-ethylphenol (4-EP). Phenol conversion increases by increasing temperature up to 350degreesC and then decreases at 400degreesC. There is no correlation between the acidity and activity of the catalysts. The low activity of (Al, Zn)-MCM-41(52) is due to its high hydrophilicity, which reduces the chemisorption of ethyl acetate on its surface. The low conversion of phenol at low ethyl acetate/phenol feed ratios is attributed to the preferential chemisorption of phenol on the catalyst surface. The decrease in conversion at higher temperature is due to blocking of active sites by coke. This study has revealed that ethyl acetate is an active alkylating reagent for phenol in the vapour phase. (C) 2004 Elsevier B.V. All rights reserved.