A series of Co–Ni catalysts, prepared from hydrotalcite (HT)-like materials by co-precipitation, has been studied for the hydrogen production by ethanol steam reforming. The total metal loading was fixed at 40% and the Co–Ni composition was varied (40–0, 30–10, 20–20, 10–30 and 0–40). The catalysts were characterized using X-ray diffraction, N2 physisorption, H2 chemisorption, temperature-programmed reduction, scanning transmission electron microscope and energy dispersive spectroscopy. The results demonstrated that the particle size and reducibility of the Co–Ni catalysts are influenced by the degree of formation of a HT-like structure, increasing with Co content. All the catalysts were active and stable at 575 °C during the course of ethanol steam reforming with a molar ratio of H2O:ethanol = 3:1. The activity decreased in the order 30Co–10Ni > 40Co ~ 20Ni–20Co ~ 10Co–30Ni > 40Ni. The 40Ni catalyst displayed the strongest resistance to deactivation, while all the Co-containing catalysts exhibited much higher activity than the 40Ni catalyst. The hydrogen selectivities were high and similar among the catalysts, the highest yield of hydrogen was found over the 30Co–10Ni catalyst. In general, the best catalytic performance is obtained with the 30Co–10Ni catalyst, in which Co and Ni are intimately mixed and dispersed in the HT-derived support, as indicated by the STEM micrograph and complementary mapping of Co, Ni, Al, Mg and O.