Ethanol steam reforming of synthetic bioethanol (i.e., anhydrous ethanol plus water), as well as bioethanol obtained from glucose standards and sugarcane press-mud was evaluated on monoliths washcoated with RhPt/CeO2–SiO2. Tests with synthetic bioethanol indicated that the lower pressure drop favors higher ethanol conversion in the monoliths with respect to the powder samples. Also, two monoliths in series with 0.08 gcat/cm3 improved H2 yield compared to just one monolith with 0.16 gcat/cm3. Similarly, a decrease in the amount of carrier gas contributes to diffusion limitations in the monoliths, reducing the H2/CO ratio. Monoliths stability was also evaluated with “real” bioethanol samples (from glucose standards and sugarcane press-mud-SPM). In all cases, a syngas with >60% of H2 was produced. For SPM-bioethanol, 3.1 ± 0.2 mol H2/mol EtOH were obtained without evidence of deactivation for 120 h, at a cost of 6.9 $/kgH2, becoming a promising way to develop a technology for sustainable energy production.