Abstract Vapour phase dehydration of dilute bio-ethanol (EtOH) to ethylene (E) and diethyl ether (DEE) is industrially relevant. Ethylene is an important raw material for many petrochemical products and Diethyl ether (DEE) can be used as an alternative fuel. The efficacy of montmorillonite (K-10) and dodecatungestophosphoric acid (DTPA) supported on montmorillonite (DTPA/K-10), has been evaluated in the current work in the dehydration of dilute bio-ethanol (80% m/m). The dehydration of ethanol and cracking of diethyl ether were studied independently. 30% m/m DTPA/K-10 was found to be more active with 74% ethanol conversion and 92% ethylene selectivity at 250 °C in comparison with other acid catalysts used. The merit of the process lies in its use of dilute bio-ethanol, a new avenue for ethylene production from a non-petroleum feedstock. Kinetic interpretation has been made by studying the important process parameters by using 30% m/m DTPA/montmorillonite as the catalyst. The mechanism of the dehydration of ethanol reaction suggests that two types of sites are responsible. The dehydration of ethanol and cracking of diethyl ether are second order reactions with weak adsorption of species.