Porous clay heterostructures were prepared from Al-intercalated clays, and they allowed the insertion of Al into the framework of intercalated silica in porous clay heterostructures (PCHs). This method has led to tuneable Al contents within the resulting porous clay heterostructures. X-ray fluorescence confirmed the presence of Al in the intercalated precursors and their derivatives (porous clay heterostructure materials) in various environments, as indicated by 27Al magic-angle spinning nuclear magnetic resonance. The Al porous clay heterostructures exhibited specific surface areas that varied from 743 to 850 m2/g with total acid concentrations which varied from 0.969 to 1.420 mmol of protons/g of material, values which were deduced from the temperature desorption of cyclohexylamine. These acid sites were sufficiently strong to initiate the hydro-isomerization of n-heptane. The catalytic properties of the porous clay heterostructures depended on the Al contents and reached a maximum conversion rate of 50% and an isomer selectivity of 70% at a test reaction temperature of 350°C.