Solid acid catalysts are extensively used in a number of industrially important catalytic reactions. Here, waterinsoluble novel mesoporous solid acid catalysts, with a unique structure composed of WOx nanorods and W nanoballs within an amorphous silicate lattice, were synthesized following a one-pot hydrothermal route, using silicotungstic acid (STA) as the active component. Surface area of these catalysts are more than 2 orders of magnitude higher than that of pure STA, and they showed very high activity for the simultaneous production of ethylene and diethylether (DEE), which is an attractive transportation fuel alternate, from a nonpetroleum feedstock, namely ethanol. Depending upon the operating conditions, ethylene or DEE selectivities approaching 1.0 or 0.8 were obtained, respectively. © 2009 American Chemical Society.