The catalytic activity of Pt and PtNi catalysts supported on γ-Al2O3 modified by La and Ce oxides was investigated in the steam reforming of ethanol/glycerol mixtures. In general, all the catalysts fully converted the glycerol at the temperatures tested. However, the conversion of ethanol depended on the reaction temperature and catalyst type. The conversion into gaseous products operating at 500 °C and 450 °C was 100% using the most active catalysts (PtNiAl6La and PtNiAl10Ce). These two bimetallic catalysts gave H2 yields close to those predicted by thermodynamic equilibrium at these temperatures. However, when the reaction temperature was lowered to 400 °C, these catalytic systems and the PtNiAl one recorded a significant decrease in ethanol conversion and H2 yield, which moved away from the thermodynamic equilibrium value. This deviation was due to intermediate liquid products (acetaldehyde, acrolein, etc.) not being further reformed and the formation of other gaseous ones (light alkanes and ethylene). PtNiAl10Ce catalyst presented the highest conversion into gas at 400 °C, resulting in the largest H2 yield, followed by PtNiAl6La and PtNiAl catalysts. This order is in agreement with the Ni/Al surface atomic ratio measured by XPS technique in reduced samples. However, filamentous carbon nanotubes were detected but this carbon type maintained the active sites accessible for reactants, since TEM and TGA results showed that the density of this carbon was lower for PtNiAl10Ce catalyst. Pt catalysts presented lower activity than PtNi catalysts possibly due to the formation of carbon nanotubes, which covered some metallic active sites. Display omitted ► H2 production from ethanol/glycerol mixtures SR on Pt & PtNi systems was studied. ► Pt–Ni cooperative effect provides a better performance for the bimetallic catalysts. ► PtNiAl10Ce showed good performance due to higher Ni exposure and lower coke amount. ► CeO2 seems to removal carbon from the support. ► PtNi catalysts promote filamentous while Pt counterparts are partially covered by CNTs.