Very high ethylene selectivity values approaching 100% and very high ethanol conversion values approaching 85% were obtained in dehydration of ethanol over a new W-silicate-based nanocomposite catalyst having both meso and macropores and containing a W/Si atomic ratio of 0.85. Silicotungsticacid was successfully incorporated into the catalyst structure following a one-pot hydrothermal synthesis procedure. This catalyst is highly stable and does not loose activity in polar solvents and it has a sufficiently high surface area for catalytic applications. Calcination temperature of the catalyst was found to have a very significant effect on the catalyst structure and also on its catalytic performance in ethanol dehydration. Maximum selectivity of the second major reaction product diethylether was obtained as 0.7 at 200 °C, with the catalyst which was calcined at 400 °C. Very high ethylene and diethylether yield values obtained in this study at different reaction conditions are highly promising for the production of petrochemicals from ethanol. © 2009 Elsevier Ltd. All rights reserved.