Glass-ceramic foams belonging to the LZSA (Li2O-ZrO2-SiO2-Al2O3) system were processed as catalytic supports for the ethanol decomposition. The active phases of the support (Ni, Co) were prepared by wet impregnation. The impregnated supports were dried, calcined and reduced under a H2 flow at 700 °C for 120 min. The catalytic activity tests were performed at 550 °C for 120 min in a tubular fixed bed reactor at atmospheric pressure, with flow rate of liquid ethanol and gaseous nitrogen of 0.08 mL/min and 33.5 mL/min, respectively. The materials were characterized in terms of their physical, morphological and microstructural, thermal and mechanical properties. The results showed that the supported nickel catalysts presented a higher conversion of ethanol to form hydrogen.