Commercial high-pore-volume alumina and La-doped aluminas have been characterized and tested as catalysts for ethanol conversion to ethylene and diethyl ether and for diethyl ether cracking. In order to go deeper on reaction paths and mechanisms, steady state, TPSR and static experiments in an IR cell were performed. It is established that ethylene forms from ethanol by two parallel ways: i) cracking of ethoxy groups that occurs already at low temperature, and ii) the parallel synthesis and cracking of DEE at intermediate temperatures. Coordination of diethyl ether on Lewis sites represents the first step in its decomposition path. Lewis bonded DEE first cracks to ethoxy species and ethylene gas, while ethoxy species in part crack to a second step to another ethylene gas molecule and in part (only at low temperature) can desorb as gaseous ethanol. Commercial low loading lanthanum-doped alumina contain dispersed La3+-O2- species mainly interacting with the most reactive defect, edge and corner sites of alumina nanocrystals. At higher loading (4 wt% La2O3) very small LaxOy clusters also appear. Lanthanum doping slightly reduces the number of active sites for ethanol dehydration as well as for DEE cracking, thus reducing catalytic activity, but does not modify significantly selectivities and ethylene yields at high temperature. However, it also considerably reduces the amount of carbonaceous residues formed upon both reactions over the catalyst. Thus, La-doping is proposed as a way to improve the alumina catalyst stability in the process. Catalytic cracking of DEE at 673 K does not represent a good way to remove odorous and dense DEE vapours from air, due to the coproduction of small amounts of acetaldehyde together with ethylene.