Ethanol steam reforming is an interesting alternative for hydrogen production since ethanol can be renewably obtained. Use of lamellar double hydroxides (LDHs) as precursors of nickel catalysts leads to highly dispersed metal particles in an aluminium structure. In this sense, a Ni(II)Al(III) catalyst was synthesized from a LDH precursor and tested in ethanol steam reforming. Although this catalyst presents high stability, acidity of alumina promotes carbon deposition from ethylene through ethanol dehydration. For this reason, in order to neutralize acid sites, a series of catalysts was prepared by Mg addition to LDH precursors varying Mg/Ni ratio. The effect of Mg/Ni ratio in the catalyst on coke formation during ethanol steam reforming was studied, resulting in significant reduction of the amount of deposited carbon for Mg/Ni ratio higher than 0.1. Moreover, Mg addition increases the catalytic activity due to lower ethylene formation, which competes with ethanol for the same Ni active sites.