Mesoporous silica-supported metals are often used as catalysts in the steam reforming of hydrocarbons to produce hydrogen or syngas. In the current study, the steam reforming of ethanol was undertaken using mesoporous cellular foam silica (MCF) and SBA-15 as supports with bimetals Cu and Co in different proportions. Among these 20% Cu–Co (1:1)/MCF was found to be superior exhibiting good activity and stability for hydrogen production. Thereafter, Ce was introduced to reduce coke deposition on the said catalyst. Amongst all synthesized catalysts 5%Ce–10%Cu–10%Co/MCF led to higher hydrogen yield (82.1%) with 97.4% conversion of ethanol at a lower temperature (673 K) using steam to carbon (S/C) ratio of 6. The effect of temperature, GHSV, and S/C ratio on H2 production was systematically examined. Ce-promoted Cu–Co/MCF provided high stability for three cycles, indicating its multi-cycle durability and selectivity. 5%Ce–10%Cu–10%Co/MCF produces hydrogen from ethanol in a sustainable way.