During steam reforming, the performance of a catalyst and amount/property of coke are closely related to reaction intermediates reaching surface of a catalyst. Herein, modification of reaction intermediates by placing Mg-Al-hydrotalcite above Ni/KIT-6 catalyst in steam reforming of glycerol was conducted at 300 to 600 °C. The results revealed that the catalytic activity of Ni/KIT-6 in the lower bed was enhanced with either Mg₁-Al₅-hydrotalcite (containing more acidic sites) or Mg₅-Al₁-hydrotalcite (containing more alkaline sites) as upper-layer catalyst. The in situ infrared characterization of steam reforming demonstrated that Mg-Al-hydrotalcite catalyzed the deoxygenation of glycerol, facilitating the reforming of the partially deoxygenated intermediates over Ni/KIT-6. Mg-Al-hydrotalcite as protective catalyst, however, did not protect the Ni/KIT-6 from formation of more coke. Nonetheless, this did not lead to further deactivation of Ni/KIT-6 while Mg₅-Al₁-hydrotalcite even substantially enhanced the catalytic stability, even though the coke was much more significant than that in the use of single Ni/KIT-6 (52.7% vs. 28.6%). The reason beneath this was change of the property of coke from more aliphatic to more aromatic. Mg₅-Al₁-hydrotalcite catalyzed dehydration of glycerol, producing dominantly reaction intermediates bearing C=C, which formed the catalytic coke of with carbon nanotube as the main form with smooth outer walls as well as higher aromaticity, C/H ratio, crystallinity, crystal carbon size, thermal stability, and resistivity toward oxidation on Ni/KIT-6 in the lower bed. In comparison, the abundance of acidic sites on Mg₁-Al₅-hydrotalcite catalyzed the formation of more oxygen-containing species, leading to the formation of carbon nanotubes of rough surface on Ni/KIT-6.